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CN110914757B - Photosensitive or radiation-sensitive resin composition, resist film, pattern forming method, and method for manufacturing solid-state imaging element - Google Patents

Photosensitive or radiation-sensitive resin composition, resist film, pattern forming method, and method for manufacturing solid-state imaging element Download PDF

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Publication number
CN110914757B
CN110914757B CN201880047273.8A CN201880047273A CN110914757B CN 110914757 B CN110914757 B CN 110914757B CN 201880047273 A CN201880047273 A CN 201880047273A CN 110914757 B CN110914757 B CN 110914757B
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China
Prior art keywords
group
radiation
actinic
ray
resin composition
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CN201880047273.8A
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CN110914757A (en
Inventor
东耕平
高桑英希
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Fujifilm Corp
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Fujifilm Corp
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    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/039—Macromolecular compounds which are photodegradable, e.g. positive electron resists
    • G03F7/0392—Macromolecular compounds which are photodegradable, e.g. positive electron resists the macromolecular compound being present in a chemically amplified positive photoresist composition
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/038—Macromolecular compounds which are rendered insoluble or differentially wettable
    • G03F7/0382—Macromolecular compounds which are rendered insoluble or differentially wettable the macromolecular compound being present in a chemically amplified negative photoresist composition
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/0045—Photosensitive materials with organic non-macromolecular light-sensitive compounds not otherwise provided for, e.g. dissolution inhibitors
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/039—Macromolecular compounds which are photodegradable, e.g. positive electron resists
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/039—Macromolecular compounds which are photodegradable, e.g. positive electron resists
    • G03F7/0392—Macromolecular compounds which are photodegradable, e.g. positive electron resists the macromolecular compound being present in a chemically amplified positive photoresist composition
    • G03F7/0397—Macromolecular compounds which are photodegradable, e.g. positive electron resists the macromolecular compound being present in a chemically amplified positive photoresist composition the macromolecular compound having an alicyclic moiety in a side chain
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/09—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers
    • G03F7/11—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers having cover layers or intermediate layers, e.g. subbing layers
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/20—Exposure; Apparatus therefor
    • G03F7/2002—Exposure; Apparatus therefor with visible light or UV light, through an original having an opaque pattern on a transparent support, e.g. film printing, projection printing; by reflection of visible or UV light from an original such as a printed image
    • G03F7/2012—Exposure; Apparatus therefor with visible light or UV light, through an original having an opaque pattern on a transparent support, e.g. film printing, projection printing; by reflection of visible or UV light from an original such as a printed image using liquid photohardening compositions, e.g. for the production of reliefs such as flexographic plates or stamps
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
    • H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic Table or AIIIBV compounds with or without impurities, e.g. doping materials
    • H01L21/26—Bombardment with radiation
    • H01L21/263—Bombardment with radiation with high-energy radiation
    • H01L21/265—Bombardment with radiation with high-energy radiation producing ion implantation
    • H01L21/266—Bombardment with radiation with high-energy radiation producing ion implantation using masks
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L27/00—Devices consisting of a plurality of semiconductor or other solid-state components formed in or on a common substrate
    • H01L27/14—Devices consisting of a plurality of semiconductor or other solid-state components formed in or on a common substrate including semiconductor components sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation
    • H01L27/144—Devices controlled by radiation
    • H01L27/146—Imager structures
    • H01L27/14601—Structural or functional details thereof
    • H01L27/1462—Coatings
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L27/00—Devices consisting of a plurality of semiconductor or other solid-state components formed in or on a common substrate
    • H01L27/14—Devices consisting of a plurality of semiconductor or other solid-state components formed in or on a common substrate including semiconductor components sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation
    • H01L27/144—Devices controlled by radiation
    • H01L27/146—Imager structures
    • H01L27/14683—Processes or apparatus peculiar to the manufacture or treatment of these devices or parts thereof
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L27/00—Devices consisting of a plurality of semiconductor or other solid-state components formed in or on a common substrate
    • H01L27/14—Devices consisting of a plurality of semiconductor or other solid-state components formed in or on a common substrate including semiconductor components sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation
    • H01L27/144—Devices controlled by radiation
    • H01L27/146—Imager structures
    • H01L27/14683—Processes or apparatus peculiar to the manufacture or treatment of these devices or parts thereof
    • H01L27/14685—Process for coatings or optical elements
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/20—Filters
    • G02B5/208—Filters for use with infrared or ultraviolet radiation, e.g. for separating visible light from infrared and/or ultraviolet radiation
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/16—Coating processes; Apparatus therefor
    • G03F7/162—Coating on a rotating support, e.g. using a whirler or a spinner
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/16—Coating processes; Apparatus therefor
    • G03F7/168—Finishing the coated layer, e.g. drying, baking, soaking
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/20—Exposure; Apparatus therefor
    • G03F7/2002—Exposure; Apparatus therefor with visible light or UV light, through an original having an opaque pattern on a transparent support, e.g. film printing, projection printing; by reflection of visible or UV light from an original such as a printed image
    • G03F7/2004—Exposure; Apparatus therefor with visible light or UV light, through an original having an opaque pattern on a transparent support, e.g. film printing, projection printing; by reflection of visible or UV light from an original such as a printed image characterised by the use of a particular light source, e.g. fluorescent lamps or deep UV light
    • G03F7/2006—Exposure; Apparatus therefor with visible light or UV light, through an original having an opaque pattern on a transparent support, e.g. film printing, projection printing; by reflection of visible or UV light from an original such as a printed image characterised by the use of a particular light source, e.g. fluorescent lamps or deep UV light using coherent light; using polarised light
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/26—Processing photosensitive materials; Apparatus therefor
    • G03F7/30—Imagewise removal using liquid means
    • G03F7/32—Liquid compositions therefor, e.g. developers
    • G03F7/322—Aqueous alkaline compositions
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/26—Processing photosensitive materials; Apparatus therefor
    • G03F7/38—Treatment before imagewise removal, e.g. prebaking
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/26—Processing photosensitive materials; Apparatus therefor
    • G03F7/40—Treatment after imagewise removal, e.g. baking

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  • Engineering & Computer Science (AREA)
  • Power Engineering (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Computer Hardware Design (AREA)
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Abstract

The present invention provides a actinic-ray-or radiation-sensitive resin composition capable of forming a pattern capable of suppressing ion leakage in an ion implantation process. Also provided are a resist film and a pattern forming method using the actinic-ray-sensitive or radiation-sensitive resin composition. And a method for manufacturing a solid-state imaging element using the pattern forming method. The actinic-ray-or radiation-sensitive resin composition for forming a pattern to be used as a mask in an ion implantation process, the composition comprising: a resin comprising a repeating unit having an acid-decomposable group; a photoacid generator; and an additive having a melting point or glass transition temperature of less than 25 ℃ and a molecular weight of 180 or more, wherein the content of the additive is 1 mass% or more relative to the total solid content in the composition.

Description

Photosensitive or radiation-sensitive resin composition, resist film, pattern forming method, and method for manufacturing solid-state imaging element
Technical Field
The present invention relates to a actinic-ray-or radiation-sensitive resin composition, a resist film, a pattern forming method, and a method for manufacturing a solid-state imaging device.
Background
A CCD (Charge-Coupled Device) or CMOS (Complementary Metal Oxide Semiconductor: complementary metal oxide semiconductor) that is a solid-state imaging element for color images is used for a video camera, a digital camera (Digital Still Camera), a mobile phone with camera function, and the like.
These solid-state imaging devices have two-dimensionally arranged light receiving units, and the light receiving units photoelectrically convert incident light to generate electronic image signals. The light receiving section itself has sensitivity not only in the entire visible light region (380 nm to 780 nm) but also in the near infrared region of long wavelength (wavelength of about 2500 nm). The solid-state imaging device further includes a plurality of color filter layers, infrared ray transmission filter layers, and the like having different transmission wavelength regions on the light receiving surface.
A semiconductor substrate having a power storage layer with sensitivity at a predetermined wavelength is used for the light receiving section. The above-described electric storage layer is generally formed by the following method: a pattern is formed on a semiconductor substrate using a resist composition, the pattern is used as a mask, and ions (impurities) are implanted into a non-mask region of the semiconductor substrate using an ion implantation device. In order to obtain a light receiving section having sufficient sensitivity to light having a long wavelength such as infrared rays, it is necessary to implant impurities into deep positions of a semiconductor substrate by performing Ion Implantation (hereinafter, also referred to as "Ion Implantation") at high energy. When ion implantation is performed at high energy, a thick film pattern is used.
For example, patent document 1 discloses, as a resist composition capable of forming a thick film pattern, a "positive resist composition for forming a thick film resist film having a film thickness of 1 to 15 μm, which is characterized in that the positive resist composition is formed by dissolving a resin component (a) having increased alkali solubility due to the action of an acid and an acid generator component (B) generating an acid by exposure in an organic solvent (S), wherein the organic solvent (S) is a mixed solvent of 10 to 95 mass% of propylene glycol monomethyl ether and 5 to 90 mass% of other solvent (S2). ".
Technical literature of the prior art
Patent literature
Patent document 1: japanese patent No. 4954576
Disclosure of Invention
Technical problem to be solved by the invention
The present inventors have attempted to implant ions (impurities) into a semiconductor substrate using a thick film pattern formed from the positive resist composition described in patent document 1 as a mask. As a result, when ions are implanted to a depth at which sufficient sensitivity can be imparted to infrared rays in practical use, it was confirmed that ion leakage occurred in the mask region of the semiconductor substrate. That is, it was confirmed that the emitted ions were transmitted through the mask and were also implanted into the semiconductor substrate below the mask.
Accordingly, an object of the present invention is to provide a actinic ray-or radiation-sensitive resin composition capable of forming a pattern capable of suppressing ion leakage in an ion implantation step.
The present invention also provides a resist film and a pattern forming method using the above-mentioned actinic-radiation-sensitive or radiation-sensitive resin composition.
The present invention also provides a method for manufacturing a solid-state imaging element using the above-described pattern formation method.
Means for solving the technical problems
As a result of intensive studies to achieve the above-mentioned object, the present inventors have found that the above-mentioned object can be achieved by containing a predetermined additive in a actinic-ray-or radiation-sensitive resin composition, and have completed the present invention.
That is, it has been found that the above object can be achieved by the following constitution.
[ 1 ] A actinic-ray-or radiation-sensitive resin composition for forming a pattern to be used as a mask in an ion implantation process, the composition comprising:
a resin comprising a repeating unit having an acid-decomposable group;
a photoacid generator; and
Additives having a melting point or glass transition temperature of less than 25 ℃ and a molecular weight of 180 or more,
The content of the additive is 1% by mass or more relative to the total solid content in the composition.
The actinic-ray-or radiation-sensitive resin composition according to [ 1 ], wherein the pattern has a film thickness of 5 μm or more.
The actinic-ray-or radiation-sensitive resin composition according to [ 1 ] or [ 2 ], wherein the pattern has a film thickness of 7 μm or more.
The actinic-ray-or radiation-sensitive resin composition according to any one of [ 1 ] to [ 3 ], wherein the solid content concentration in the composition is 20% by mass or more.
The actinic-ray-or radiation-sensitive resin composition according to any one of [ 1 ] to [ 4 ], wherein a film density of a film having a film thickness of 9 μm obtained by applying the actinic-ray-or radiation-sensitive resin composition onto a substrate to form a coating film and then baking the coating film at 150℃for 90 seconds is 1.05g/cm 3 The above.
The actinic-ray-or radiation-sensitive resin composition according to [ 5 ], wherein the film density is 1.10g/cm 3 The above.
The actinic-ray-or radiation-sensitive resin composition according to any one of [ 1 ] to [ 6 ], wherein the glass transition temperature of the resin is 170℃or lower.
The actinic-ray-or radiation-sensitive resin composition according to any one of [ 1 ] to [ 7 ], wherein the additive is water-soluble.
The actinic-ray-or radiation-sensitive resin composition according to any one of [ 1 ] to [ 8 ], wherein the ion implantation step is an ion implantation step for forming the light receiving section for the infrared-ray-transmitting filter in the production of a solid-state imaging element including an infrared-ray-transmitting filter that selectively transmits an infrared component.
[ 10 ] A resist film formed of the actinic-ray-or radiation-sensitive resin composition according to any one of [ 1 ] to [ 9 ].
[ 11 ] a pattern forming method comprising: a resist film forming step of forming a resist film using the actinic-ray-or radiation-sensitive resin composition according to any one of [ 1 ] to [ 9 ]; an exposure step of exposing the resist film; and a developing step of developing the exposed resist film using a developer.
[ 12 ] a method for manufacturing a solid-state imaging element, which includes the pattern forming method described in [ 11 ], the method comprising:
An ion implantation step of forming a light receiving section for sensing infrared rays by implanting ions into a non-mask region of a substrate with the pattern formed on the substrate as a mask;
removing the pattern from the substrate; and
An infrared ray transmissive filter layer arrangement step of arranging an infrared ray transmissive filter layer on the ion-implanted region of the substrate.
Effects of the invention
According to the present invention, a actinic-ray-or radiation-sensitive resin composition capable of forming a pattern capable of suppressing ion leakage in an ion implantation process can be provided.
Further, according to the present invention, a resist film and a pattern forming method using the above-mentioned actinic-radiation-sensitive or radiation-sensitive resin composition can be provided.
Further, according to the present invention, a method for manufacturing a solid-state imaging device using the above-described pattern formation method can be provided.
Detailed Description
The present invention will be described in detail below.
The explanation of the constituent elements described below is sometimes made based on the representative embodiments of the present invention, but the present invention is not limited to such embodiments.
The term "actinic rays" or "radiation" in the present specification means, for example, an open line spectrum of a mercury lamp, extreme ultraviolet rays typified by excimer laser, extreme ultraviolet rays (EUV light: extreme Ultraviolet), X-rays, electron beams (EB: electron Beam), and the like. The term "light" as used herein means actinic rays or radiation.
The term "exposure" in the present specification includes, unless otherwise specified, not only exposure by an open line spectrum using a mercury lamp, extreme ultraviolet rays typified by excimer laser, extreme ultraviolet rays, X-rays, EUV light, and the like, but also drawing by a particle beam such as an electron beam and an ion beam.
In the present specification, "to" is used in a sense including numerical values before and after the description as a lower limit value and an upper limit value.
In the present specification, (meth) acrylate means acrylate and methacrylate.
In the present specification, the weight average molecular weight (Mw), the number average molecular weight (Mn), and the dispersity (hereinafter, also referred to as molecular weight distribution.) (Mw/Mn) of the resin are defined as polystyrene conversion values based on GPC measurement (solvent: tetrahydrofuran, flow rate (sample injection amount): 10. Mu.L, column: TSK gel Multipore HXL-M manufactured by TOSOH CORPORATION, column temperature: 40 ℃, flow rate: 1.0 mL/min, detector: differential refractive index detector (Refractive Index Detector)) of GPC (gel permeation chromatography (Gel Permeation Chromatography)) apparatus (HLC-8120 GPC) manufactured by TOSOH CORPORATION).
Regarding the labeling of groups (atomic groups) in the present specification, the label which is not labeled with a substituted and unsubstituted includes a group having no substituent, and also includes a group having a substituent. For example, "alkyl" includes not only an alkyl group having no substituent (unsubstituted alkyl group) but also an alkyl group having a substituent (substituted alkyl group). In the present specification, the term "organic group" means a group containing at least one carbon atom.
In the present specification, the type of substituent, the position of the substituent, and the number of substituents when referred to as "substituent may be provided" are not particularly limited. The number of substituents may be, for example, 1, 2, 3 or more. Examples of the substituent include a 1-valent nonmetallic atom group other than a hydrogen atom, and for example, the substituent group T may be selected from the following groups.
(substituent T)
Examples of the substituent T include halogen atoms such as fluorine atom, chlorine atom, bromine atom and iodine atom; alkoxy groups such as methoxy, ethoxy and t-butoxy; aryloxy groups such as phenoxy and p-tolyloxy; alkoxycarbonyl groups such as methoxycarbonyl, butoxycarbonyl and phenoxycarbonyl; acyloxy groups such as acetoxy, propionyloxy and benzoyloxy; acyl groups such as acetyl, benzoyl, isobutyryl, acryl, methacryl, and methionyl (methoxalyl group); alkylthio groups such as methylthio (sulfoxyl goup) and tert-butylthio; arylthio groups such as phenylthio and p-tolylthio; an alkyl group; cycloalkyl; an aryl group; heteroaryl; a hydroxyl group; a carboxyl group; a formyl group; a sulfo group; cyano group; an alkylaminocarbonyl group; an arylaminocarbonyl group; sulfonamide groups; silicon-based; an amino group; a monoalkylamino group; a dialkylamino group; an arylamino group; and combinations of these.
[ photosensitive radiation-sensitive or radiation-sensitive resin composition ]
The actinic ray-sensitive or radiation-sensitive resin composition of the present invention may be characterized by containing a predetermined amount of a specific additive to the total solid content in the composition.
The present inventors have found that the above-described problem of ion leakage is associated with residual solvents remaining in the interior of a pattern formed of a actinic ray-sensitive or radiation-sensitive resin composition. Specifically, it is considered that the more residual solvent remains in the pattern, the lower the film density of the pattern, and as a result, ion leakage occurs in the ion implantation step.
The inventors of the present invention have found that the above-mentioned problems of the conventional arts can be solved by blending a predetermined amount of the above-mentioned specific additive into the actinic ray-or radiation-sensitive resin composition. The above-mentioned specific additive has an effect of improving the plasticity of the resist film (in other words, the film of the actinic ray-sensitive or radiation-sensitive resin composition) in the resist film. Therefore, it is presumed that the solvent remaining in the resist film is easily volatilized due to the presence of the specific additive, and as a result, the film density of the formed pattern is excellent.
According to the pattern formed by the actinic ray-sensitive or radiation-sensitive resin composition of the present invention, by the above mechanism of action, ion leakage can be suppressed even in the case where ions are injected with high energy in the ion injection step.
Hereinafter, the components contained in the actinic ray-sensitive or radiation-sensitive resin composition of the present invention (hereinafter, also referred to as "the composition of the present invention") will be described in detail. The composition of the present invention is a so-called resist composition, and may be a positive resist composition or a negative resist composition. The resist composition may be an alkaline development resist composition or an organic solvent development resist composition. Among them, a positive resist composition and a resist composition for alkali development are preferable.
The composition of the present invention is typically a chemically amplified resist composition.
< resin (A) >)
The composition of the present invention contains a resin (hereinafter, also referred to as "resin (a)") containing a repeating unit having an acid-decomposable group.
In this case, in the pattern forming method of the present invention, typically, when an alkaline developer is used as the developer, a positive pattern is preferably formed, and when an organic developer is used as the developer, a negative pattern is preferably formed.
Further, in terms of further excellent film density of the formed pattern and further suppression of ion leakage in the ion implantation step, the glass transition temperature (Tg (°c)) of the resin (a) is preferably 170 ℃ or less, more preferably 140 ℃ or less. In general, the lower limit of the glass transition temperature of the resin (A) is 100℃or higher.
When there is a catalogue value or a literature value, the glass transition temperature of the resin (a) is measured by a differential scanning calorimetry (DSC: differential scanning calorimetry) method when there is no catalogue value or literature value.
When the resin (a) is a copolymer and there is no catalogue value or literature value, the glass transition temperature can be calculated by the following formula (1).
1/(273+Tg) =Σ (Wi/(273+Tgi))
Tg: glass transition temperature (. Degree. C.) of resin (A)
Tgi: glass transition temperature (. Degree. C.) of homopolymer of monomer i
Wi: mass ratio of monomer i. And Σwi=1.
(repeating units having acid-decomposable groups)
The resin (a) contains a repeating unit having an acid-decomposable group (hereinafter, also referred to as "repeating unit X1").
The acid-decomposable group is preferably a group which is decomposed by the action of an acid to generate a polar group.
Examples of the polar group include an acidic group (a group dissociated from 2.38 mass% aqueous tetramethylammonium hydroxide solution) such as a carboxyl group, a phenolic hydroxyl group, a fluorinated alcohol group, a sulfonic acid group, a sulfonamide group, a sulfonylimide group, an (alkylsulfonyl) (alkylcarbonyl) methylene group, an (alkylsulfonyl) (alkylcarbonyl) imide group, a bis (alkylsulfonyl) methylene group, a bis (alkylsulfonyl) imide group, a tris (alkylcarbonyl) methylene group, and a tris (alkylsulfonyl) methylene group, and an alcoholic hydroxyl group.
The alcoholic hydroxyl group is a hydroxyl group bonded to a hydrocarbon group, and means a hydroxyl group other than a hydroxyl group directly bonded to an aromatic ring (phenolic hydroxyl group), and as a hydroxyl group, an aliphatic alcohol having an α -position substituted with an electron withdrawing group such as a fluorine atom (for example, hexafluoroisopropanol group or the like) is excluded. The alcoholic hydroxyl group is preferably a hydroxyl group having a pKa (acid dissociation constant) of 12 to 20 inclusive.
Preferred polar groups include carboxyl groups, phenolic hydroxyl groups, fluorinated alcohol groups (preferably hexafluoroisopropanol groups), and sulfonic acid groups.
The acid-decomposable group is preferably a group in which a hydrogen atom of a polar group is substituted with a group (a release group) released by the action of an acid.
Examples of the group (releasing group) released by the action of an acid include-C (R) 36 )(R 37 )(R 38 )、-C(R 36 )(R 37 )(OR 39 ) -C (R) 01 )(R 02 )(OR 39 ) Etc.
Wherein R is 36 ～R 39 Each independently represents an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group or an alkenyl group. R is R 36 And R is R 37 Can be bonded to each other to form a ring.
R 01 R is R 02 Each independently represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group or an alkenyl group.
R 36 ～R 39 、R 01 R is R 02 The alkyl group of (a) is preferably an alkyl group having 1 to 8 carbon atoms, and examples thereof include methyl, ethyl, propyl, n-butyl, sec-butyl, hexyl, octyl, and the like.
R 36 ～R 39 、R 01 R is R 02 The cycloalkyl group of (2) may be a single ring or multiple rings. The monocyclic cycloalkyl group is preferably a cycloalkyl group having 3 to 8 carbon atoms, and examples thereof include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, and cyclooctyl groups. The polycyclic cycloalkyl group is preferably a cycloalkyl group having 6 to 20 carbon atoms, and examples thereof include adamantyl, norbornyl, isobornyl, camphene, dicyclopentanyl, α -pinenyl (pinel group), tricyclodecyl, tetracyclododecyl, and androstanyl (androstanil group). In addition, at least one carbon atom in the cycloalkyl group may be substituted with a hetero atom such as an oxygen atom.
R 36 ～R 39 、R 01 R is R 02 The aryl group of (a) is preferably an aryl group having 6 to 10 carbon atoms, and examples thereof include phenyl, naphthyl and anthracenyl.
R 36 ～R 39 、R 01 R is R 02 The aralkyl group of (a) is preferably an aralkyl group having 7 to 12 carbon atoms, and examples thereof include benzyl, phenethyl, naphthylmethyl and the like.
R 36 ～R 39 、R 01 R is R 02 The alkenyl group of (2) is preferably a C2-8 alkenyl group, and examples thereof include vinyl, allyl, butenyl, and cyclohexenyl.
As R 36 And R is R 37 The ring formed by bonding is preferably a cycloalkyl group (monocyclic or polycyclic). The cycloalkyl group is preferably a monocyclic cycloalkyl group such as cyclopentyl or cyclohexyl, or a norbornyl group, a tetracyclodecyl group, or a tetracyclododecyl groupPolycyclic cycloalkyl groups such as alkyl and adamantyl.
The acid-decomposable group is preferably a cumyl ester group (cumylester group), an enol ester group, an acetal ester group or a tertiary alkyl ester group, more preferably an acetal group or a tertiary alkyl ester group.
Repeating units having a structure in which-COOH groups are protected by a releasing group (acid-decomposable group)
The resin (a) preferably has a repeating unit represented by the following general formula (AI) as the repeating unit X1.
[ chemical formula 1]
In the general formula (AI) as described above,
Xa 1 represents a hydrogen atom, a halogen atom or a 1-valent organic group.
T represents a single bond or a 2-valent linking group.
Rx 1 ～Rx 3 Each independently represents an alkyl group or a cycloalkyl group.
Rx 1 ～Rx 3 Any 2 of them may be bonded to form a ring structure, or may not be bonded to form a ring structure.
Examples of the linking group having a valence of 2 for T include an alkylene group, an arylene group, -COO-Rt-and-O-Rt-group. Wherein Rt represents an alkylene group, a cycloalkylene group or an arylene group.
T is preferably a single bond or-COO-Rt-. Rt is preferably a chain alkylene group having 1 to 5 carbon atoms, more preferably-CH 2 -、-(CH 2 ) 2 -or- (CH) 2 ) 3 -. T is more preferably a single bond.
Xa 1 Preferably a hydrogen atom or an alkyl group.
Xa 1 The alkyl group of (a) may have a substituent, and examples of the substituent include a hydroxyl group and a halogen atom (preferably a fluorine atom).
Xa 1 The alkyl group of (a) is preferably a C1-4 alkyl group, and examples thereof include methyl, ethyl, propyl, hydroxymethyl, trifluoromethyl, and the like. Xa (Xa) 1 Preferably, the alkyl group of (a) is methyl.
As Rx 1 、Rx 2 Rx (x) 3 The alkyl group of (2) may be linear or branched, and is preferably methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl or the like. The number of carbon atoms of the alkyl group is preferably 1 to 10, more preferably 1 to 5, and still more preferably 1 to 3.Rx (x) 1 、Rx 2 Rx (x) 3 A part of the carbon-carbon bonds may be double bonds.
As Rx 1 ，Rx 2 Rx (x) 3 Preferably a monocyclic cycloalkyl group such as cyclopentyl or cyclohexyl, or a polycyclic cycloalkyl group such as norbornyl, tetracyclodecyl, tetracyclododecyl or adamantyl.
As Rx 1 、Rx 2 Rx (x) 3 The ring structure formed by bonding 2 of these are preferably a monocyclic cycloalkyl ring such as a cyclopentyl ring, a cyclohexyl ring, a cycloheptyl ring and a cyclooctane ring, or a polycyclic cycloalkyl ring such as a norbornane ring, a tetracyclodecane ring, a tetracyclododecane ring and an adamantane ring. Among them, a cyclopentyl ring, a cyclohexyl ring or an adamantane ring is more preferable. As Rx 1 、Rx 2 Rx (x) 3 The ring structure formed by bonding 2 of the above-mentioned groups is preferably as shown below.
[ chemical formula 2]
Specific examples of the monomer corresponding to the repeating unit represented by the general formula (AI) are given below, but the present invention is not limited to these specific examples. The following specific examples correspond to Xa in the general formula (AI) 1 In the case of methyl, but Xa 1 An organic group which can be optionally substituted with a hydrogen atom, a halogen atom or a valence of 1.
[ chemical formula 3]
The resin (A) also preferably has a repeating unit as the repeating unit X1 described in the paragraphs < 0336 > < 0369 > of U.S. patent application publication 2016/007067A 1.
The resin (A) may have, as the repeating unit X1, a repeating unit containing a group which is decomposed by the action of an acid to produce an alcoholic hydroxyl group as described in paragraphs < 0363 > - < 0364 > of the specification of U.S. patent application publication 2016/007067A 1.
Repeat units having a structure in which the phenolic hydroxyl groups are protected by a releasing group (acid-decomposable group)
The resin (a) also preferably contains a repeating unit having a structure in which a phenolic hydroxyl group is protected by a releasing group as the repeating unit X1. In the present specification, the phenolic hydroxyl group means a group in which a hydrogen atom of an aromatic hydrocarbon group is substituted with a hydroxyl group. The aromatic ring of the aromatic hydrocarbon group is a monocyclic or polycyclic aromatic ring, and examples thereof include a benzene ring and a naphthalene ring.
Examples of the releasing group include groups represented by the formulas (Y1) to (Y4).
Formula (Y1): -C (Rx) 1 )(Rx 2 )(Rx 3 )
Formula (Y2): -C (=o) OC (Rx 1 )(Rx 2 )(Rx 3 )
Formula (Y3): -C (R) 36 )(R 37 )(OR 38 )
Formula (Y4): c (Rn) (H) (Ar) A-5,
in the formulas (Y1) and (Y2), rx 1 ～Rx 3 Each independently represents an alkyl group (linear or branched) or a cycloalkyl group (monocyclic or polycyclic). Wherein when Rx 1 ～Rx 3 When all are alkyl groups (straight or branched), rx is preferred 1 ～Rx 3 At least 2 of which are methyl groups.
Wherein Rx is 1 ～Rx 3 More preferably each independently is a repeating unit representing a linear or branched alkyl group, rx 1 ～Rx 3 Further preferably, each independently is a repeating unit representing a linear alkyl group.
Rx 1 ～Rx 3 May be bonded to form a single ring or multiple rings.
As Rx 1 ～Rx 3 Alkyl of (2)Preferably, the alkyl group has 1 to 4 carbon atoms such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl and tert-butyl.
As Rx 1 ～Rx 3 Preferably a monocyclic cycloalkyl group such as cyclopentyl or cyclohexyl, or a polycyclic cycloalkyl group such as norbornyl, tetracyclodecyl, tetracyclododecyl, adamantyl, or the like.
As Rx 1 ～Rx 3 The cycloalkyl group bonded to 2 of the above is preferably a monocyclic cycloalkyl group such as cyclopentyl or cyclohexyl, or a polycyclic cycloalkyl group such as norbornyl, tetracyclodecyl, tetracyclododecyl or adamantyl. Among them, a monocyclic cycloalkyl group having 5 to 6 carbon atoms is more preferable.
Rx 1 ～Rx 3 Of cycloalkyl groups formed by bonding, for example, 1 of methylene groups constituting the ring may be substituted with a group having a heteroatom such as an oxygen atom or a heteroatom such as a carbonyl group.
The groups represented by the formulae (Y1) and (Y2) are preferably, for example, rx 1 Is methyl or ethyl and Rx 2 With Rx 3 Bonding to form the cycloalkyl group.
In the formula (Y3), R 36 R is R 37 Each independently represents a hydrogen atom or a 1-valent organic group. R is R 38 An organic group having a valence of 1. R is R 37 And R is R 38 Can be bonded to each other to form a ring. Examples of the 1-valent organic group include an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, an alkenyl group, and the like. R is R 36 Preferably a hydrogen atom.
In the formula (Y4), ar represents an aromatic hydrocarbon group. Rn represents alkyl, cycloalkyl or aryl. Rn and Ar may be bonded to each other to form a non-aromatic ring. Ar is more preferably aryl.
The repeating unit having a structure (acid-decomposable group) in which the phenolic hydroxyl group is protected by a releasing group is preferably a repeating unit having a structure in which a hydrogen atom in the phenolic hydroxyl group is protected by a group represented by formulae (Y1) to (Y4).
The repeating unit having a structure (acid-decomposable group) in which a phenolic hydroxyl group is protected by a releasing group is preferably a repeating unit represented by the following general formula (AII).
[ chemical formula 4]
In the general formula (AII),
R 61 、R 62 r is R 63 Each independently represents a hydrogen atom, an alkyl group, a cycloalkyl group, a halogen atom, a cyano group, or an alkoxycarbonyl group. Wherein R is 62 Can be combined with Ar 6 Bonding to form a ring, R at this time 62 Represents a single bond or an alkylene group.
X 6 Represents a single bond, -COO-or-CONR 64 -。R 64 Represents a hydrogen atom or an alkyl group.
L 6 Represents a single bond or an alkylene group.
Ar 6 An aromatic hydrocarbon group having a valence of (n+1), when combined with R 62 An aromatic hydrocarbon group having a valence of (n+2) when bonded to form a ring.
With respect to Y 2 Each of n.gtoreq.2 independently represents a hydrogen atom or a group which is detached by the action of an acid. Wherein Y is 2 Represents a group that is detached by the action of an acid. As Y 2 The groups to be released by the action of the acid are preferably of the formulae (Y1) to (Y4).
n represents an integer of 1 to 4.
Each of the above groups may have a substituent, and examples of the substituent include an alkyl group (having 1 to 4 carbon atoms), a halogen atom, a hydroxyl group, an alkoxy group (having 1 to 4 carbon atoms), a carboxyl group, and an alkoxycarbonyl group (having 2 to 6 carbon atoms), and the like, and a substituent having 8 or less carbon atoms is preferable.
Specific examples of the repeating unit represented by the general formula (AII) are shown below, but the present invention is not limited to these.
[ chemical formula 5]
[ chemical formula 6]
The resin (a) may contain 1 kind of repeating unit X1 alone or 2 or more kinds of repeating units X1 together.
The content of the repeating unit X1 (in the case where a plurality of repeating units X1 are present, the total thereof) in the resin (a) is preferably 5 mol% or more, more preferably 10 mol% or more, and still more preferably 20 mol% or more, with respect to all the repeating units of the resin (a). The upper limit of the content of the repeating unit X1 is, for example, 50 mol% or less, preferably 40 mol% or less, based on the total repeating units of the resin (a).
(other repeating units)
The resin (a) may contain other repeating units in addition to the repeating unit X1.
Hereinafter, other repeating units that the resin (a) may contain will be described in detail.
Repeat units having phenolic hydroxyl groups
The resin (a) preferably contains a repeating unit having a phenolic hydroxyl group (hereinafter, also referred to as "repeating unit X2") in addition to the repeating unit X1. In addition, the repeating unit X2 does not have an acid-decomposable group. The resin (a) is more excellent in dissolution rate in alkali development by containing the repeating unit X2.
The repeating unit X2 may be a hydroxystyrene repeating unit or a hydroxystyrene (meth) acrylate repeating unit. Among them, preferred is a repeating unit represented by the following general formula (I).
[ chemical formula 7]
In the method, in the process of the invention,
R 41 、R 42 r is R 43 Each independently represents a hydrogen atom, an alkyl group, a cycloalkyl group, a halogen atom, a cyano group or an alkoxycarbonyl group. Wherein R is 42 Can be combined with Ar 4 Bonding to form a ring, R at this time 42 Represents a single bond or an alkylene group.
X 4 Represents a single bond, -COO-or-CONR 64 -，R 64 Represents a hydrogen atom or an alkyl group.
L 4 Represents a single bond or a 2-valent linking group.
Ar 4 An aromatic hydrocarbon group having a valence of (n+1) and R 42 When bonded to form a ring, the aromatic hydrocarbon group having a valence of (n+2) is represented.
n represents an integer of 1 to 5.
For the purpose of imparting high polarity to the repeating unit represented by the general formula (I), it is also preferable that n is an integer of 2 or more or X 4 is-COO-or-CONR 64 -。
As a result of R in the general formula (I) 41 、R 42 R is R 43 The alkyl group represented is preferably an alkyl group having 20 or less carbon atoms such as a methyl group, an ethyl group, a propyl group, an isopropyl group, a n-butyl group, a sec-butyl group, a hexyl group, a 2-ethylhexyl group, an octyl group, or a dodecyl group, which may have a substituent, more preferably an alkyl group having 8 or less carbon atoms, and still more preferably an alkyl group having 3 or less carbon atoms.
As a result of R in the general formula (I) 41 、R 42 R is R 43 The cycloalkyl group may be a single ring or multiple rings. Preferred is a monocyclic cycloalkyl group having 3 to 8 carbon atoms, such as cyclopropyl, cyclopentyl, and cyclohexyl, which may have a substituent.
As a result of R in the general formula (I) 41 、R 42 R is R 43 The halogen atom represented is preferably a fluorine atom, such as a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom.
As a result of R in the general formula (I) 41 、R 42 R is R 43 The alkyl group contained in the alkoxycarbonyl group represented by the above is preferably the same as R 41 、R 42 R is R 43 The alkyl groups in (2) are the same.
Preferred substituents among the above groups include, for example, alkyl groups, cycloalkyl groups, aryl groups, amino groups, amide groups, ureido groups, urethane groups, hydroxyl groups, carboxyl groups, halogen atoms, alkoxy groups, thioether groups, acyl groups, acyloxy groups, alkoxycarbonyl groups, cyano groups, nitro groups, and the like, and the number of carbon atoms of the substituents is preferably 8 or less.
Ar 4 An aromatic hydrocarbon group having a valence of (n+1). The 2-valent aromatic hydrocarbon group in the case where n is 1 may have a substituent, and is preferably an aromatic hydrocarbon group containing an arylene group having 6 to 18 carbon atoms such as a phenylene group, a tolylene group, a naphthylene group, an anthracenyl group, or a heterocyclic ring such as thiophene, furan, pyrrole, benzothiophene, benzofuran, benzopyrrole, triazine, imidazole, benzimidazole, triazole, thiadiazole, or thiazole.
As a specific example of the (n+1) -valent aromatic hydrocarbon group in the case where n is an integer of 2 or more, a group from which (n-1) arbitrary hydrogen atoms are removed can be preferably exemplified from the above specific example of the 2-valent aromatic hydrocarbon group.
The (n+1) -valent aromatic hydrocarbon group may have a substituent.
Examples of the substituents which may be contained in the above alkyl group, cycloalkyl group, alkoxycarbonyl group and (n+1) valent aromatic hydrocarbon group include R in the general formula (I) 41 、R 42 R is R 43 An alkyl group; alkoxy groups such as methoxy, ethoxy, hydroxyethoxy, propoxy, hydroxypropoxy, and butoxy groups; aryl groups such as phenyl; etc.
As a result of X 4 represented-CONR 64 -(R 64 Represents a hydrogen atom or an alkyl group) 64 The alkyl group of (2) is preferably an alkyl group having 20 or less carbon atoms such as methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, hexyl, 2-ethylhexyl, octyl and dodecyl which may have a substituent, more preferably an alkyl group having 8 or less carbon atoms.
As X 4 Preferably a single bond, -COO-or-CONH-, more preferably a single bond or-COO-.
As L 4 The linking group having 2 valences of (2) is preferably an alkylene group, and the alkylene group is preferably an alkylene group having 1 to 8 carbon atoms such as a methylene group, a vinyl group, a propylene group, a butylene group, a hexylene group, or an octylene group, which may have a substituent.
As Ar 4 The aromatic hydrocarbon group having 6 to 18 carbon atoms which may have a substituent is preferable, and a benzene ring group, a naphthalene ring group or a biphenylene ring group is more preferable. Among them, the repeating unit represented by the general formula (I) is preferably a repeating unit derived from hydroxystyrene. Namely Ar 4 Benzene ring groups are preferred.
Hereinafter, a specific example of the repeating unit X2 is shown, but the present invention is not limited thereto. Wherein a represents 1 or 2.
[ chemical formula 8]
The resin (a) may contain 1 kind of repeating unit X2 alone or 2 or more kinds of repeating units X2 simultaneously.
The content of the repeating unit X2 (in the case where a plurality of repeating units X2 are present, the total thereof) in the resin (a) is preferably 40 mol% or more, more preferably 50 mol% or more, further preferably 60 mol% or more, preferably 85 mol% or less, more preferably 80 mol% or less, with respect to all the repeating units in the resin (a).
A repeating unit having a non-acid-decomposable chain alkyl group having 2 or more carbon atoms which may contain a hetero atom
In terms of enabling the residual solvent to be more easily volatilized, the resin (a) preferably contains a repeating unit (hereinafter, also referred to as "repeating unit X3") having a non-acid-decomposable chain alkyl group having 2 or more carbon atoms which may contain a heteroatom. The term "non-acid decomposable" means that the acid generated by the photoacid generator does not cause a separation reaction or a decomposition reaction. More specifically, the "non-acid-decomposable chain alkyl group" includes a chain alkyl group which is not separated from the resin (a) by the action of an acid which generates a photoacid generator, and a chain alkyl group which is not decomposed by the action of an acid which generates a photoacid generator.
The repeating unit X3 is preferably a repeating unit derived from a monomer having a glass transition temperature (Tg (°c)) of 50 ℃ or less (preferably 30 ℃ or less) when the monomer is a homopolymer. The lower limit is not particularly limited, but is usually-80℃or higher.
The repeating unit X3 will be described below. In the case where there is a catalogue value or a literature value, the glass transition temperature is measured by a Differential Scanning Calorimetry (DSC) method when there is no catalogue value or literature value.
The non-acid-decomposable chain alkyl group having 2 or more carbon atoms which may contain a heteroatom is not particularly limited, and examples thereof include a chain (which may be either a straight chain or a branched chain) alkyl group having 2 to 20 carbon atoms and a chain alkyl group having 2 to 20 carbon atoms which contains a heteroatom.
Examples of the chain alkyl group having 2 to 20 carbon atoms including a hetero atom include 1 or 2 or more-CH groups 2 -is interrupted by-O-, -S-, -CO-, -NR 6 Or a chain alkyl group substituted with 2-valent organic groups, in which 2 or more of these are combined. R is as described above 6 Represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.
Specific examples of the non-acid-decomposable chain alkyl group having 2 or more carbon atoms which may contain a hetero atom include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, isobutyl, sec-butyl, 1-ethylpentyl and 2-ethylhexyl groups, and 1 or 2 or more of them-CH 2 -alkyl of valence 1 substituted by-O-or-O-CO-.
In terms of the film density of the formed pattern being more excellent, the number of carbon atoms of the non-acid-decomposable chain alkyl group having 2 or more carbon atoms which may have a hetero atom is preferably 2 to 10, more preferably 2 to 8.
The non-acid-decomposable chain alkyl group having 2 or more carbon atoms may have a substituent (for example, a substituent exemplified as substituent T).
Among them, the repeating unit represented by the following general formula (1) is preferable in terms of more excellent film density of the formed pattern.
General formula (1):
[ chemical formula 9]
In the general formula (1), R 1 Represents a hydrogen atom, a halogen atom or an alkyl group. R is R 2 Represents a non-acid-decomposable chain alkyl group having 2 or more carbon atoms which may contain a hetero atom.
As represented by R 1 The halogen atom is not particularly limited, and examples thereof include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.
As represented by R 1 The alkyl group represented (may be any of linear, branched, and cyclic) is not particularly limited, and examples thereof include an alkyl group having 1 to 10 carbon atoms, specifically, methyl, ethyl, tert-butyl, and the like. Of these, alkyl groups having 1 to 3 carbon atoms are preferable, and methyl groups are more preferable.
As R 1 Among them, a hydrogen atom or a methyl group is preferable.
R 2 The definition and preferred mode of the non-acid-decomposable chain alkyl group which may contain a hetero atom and has 2 or more carbon atoms are as described above.
Examples of the monomer constituting the repeating unit X3 include ethyl acrylate (-22 ℃), n-propyl acrylate (-37 ℃), isopropyl acrylate (-5 ℃), n-butyl acrylate (-55 ℃), n-butyl methacrylate (20 ℃), n-hexyl acrylate (-57 ℃), 2-ethylhexyl acrylate (-70 ℃), isononyl acrylate (-82 ℃), lauryl methacrylate (-65 ℃), 2-hydroxyethyl acrylate (-15 ℃), 2-hydroxypropyl methacrylate (26 ℃), 1- [2- (methacryloyloxy) ethyl ] succinate (9 ℃), 2-ethylhexyl methacrylate (-10 ℃), sec-butyl acrylate (-26 ℃), methoxypolyethylene glycol monomethacrylate (n=2) (-20 ℃), cetyl acrylate (35 ℃) and 2-ethylhexyl methacrylate (-10 ℃), and the like. In addition, tg (. Degree. C.) when a homopolymer was produced is shown in parentheses.
The resin (a) may contain 1 kind of repeating unit X3 alone or 2 or more kinds of repeating units X3 together.
In the resin (a), the content of the repeating unit X3 (in the case where a plurality of repeating units X3 are present, the total thereof) is preferably 5 mol% or more, more preferably 5 to 30 mol%, and even more preferably 5 to 20 mol% with respect to all the repeating units of the resin (a).
A repeating unit having at least 1 selected from the group consisting of a lactone structure, a sultone structure, and a carbonate structure
The resin (a) preferably contains a repeating unit having at least 1 selected from the group consisting of a lactone structure, a sultone structure, and a carbonate structure (hereinafter, also referred to as "repeating unit X4").
The lactone structure or sultone structure may have a lactone structure or sultone structure, and is preferably a 5-to 7-membered ring lactone structure or a 5-to 7-membered ring sultone structure. Among them, other ring structures are more preferably condensed with 5-to 7-membered ring lactone structures in the form of a double ring structure or a spiro ring structure or other ring structures in the form of a double ring structure or a spiro ring structure, and condensed with 5-to 7-membered ring sultone structures.
More preferably, the resin (A) contains a repeating unit having a lactone structure represented by any one of the following general formulae (LC 1-1) to (LC 1-21) or a sultone structure represented by any one of the following general formulae (SL 1-1) to (SL 1-3). Also, the lactone structure or the sultone structure may be directly bonded to the main chain. Preferable structures include a lactone structure represented by the general formula (LC 1-1), the general formula (LC 1-4), the general formula (LC 1-5), the general formula (LC 1-8), the general formula (LC 1-16) or the general formula (LC 1-21), and a sultone structure represented by the general formula (SL 1-1).
[ chemical formula 10]
The lactone moiety or sultone moiety may or may not have a substituent (Rb) 2 ). As a preferred substituent (Rb) 2 ) Examples thereof include an alkyl group having 1 to 8 carbon atoms, a cycloalkyl group having 4 to 7 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, and an alkoxycarbonyl group having 2 to 8 carbon atomsThe carboxyl group, halogen atom, hydroxyl group, cyano group, acid-decomposable group and the like are preferably alkyl groups having 1 to 4 carbon atoms, cyano groups or acid-decomposable groups. n is n 2 And represents an integer of 0 to 4. When n is 2 When the number is 2 or more, a plurality of substituents (Rb 2 ) May be the same or different. And, there are a plurality of substituents (Rb 2 ) May bond to each other to form a ring.
The repeating unit having a lactone structure or a sultone structure is preferably a repeating unit represented by the following general formula (III).
[ chemical formula 11]
In the above-mentioned general formula (III),
a represents an ester bond (a group represented by-COO-or an amide bond (a group represented by-CONH) -).
n is represented by-R 0 -the number of repetitions of the structure represented by Z-represents an integer from 0 to 5, preferably 0 or 1, more preferably 0. When n is 0, no-R is present 0 Z-is a single bond.
R 0 Represents alkylene, cycloalkylene, or a combination thereof. When there are a plurality of R 0 When R is 0 Each independently represents an alkylene group, a cycloalkylene group, or a combination thereof.
Z represents a single bond, an ether bond, an ester bond, an amide bond, a urethane bond or a urea bond. When a plurality of Z are present, each Z independently represents a single bond, an ether bond, an ester bond, an amide bond, a urethane bond, or a urea bond.
R 8 Represents a 1-valent organic group having a lactone structure or a sultone structure.
R 7 Represents a hydrogen atom, a halogen atom or a 1-valent organic group (preferably a methyl group).
R 0 The alkylene or cycloalkylene group of (a) may have a substituent.
Z is preferably an ether bond or an ester bond, and more preferably an ester bond.
The resin (a) may contain a repeating unit having a carbonate structure. The carbonate structure is preferably a cyclic carbonate structure.
The repeating unit having a cyclic carbonate structure is preferably a repeating unit represented by the following general formula (A-1).
[ chemical formula 12]
In the general formula (A-1), R A 1 Represents a hydrogen atom, a halogen atom or a 1-valent organic group (preferably a methyl group).
n represents an integer of 0 or more.
R A 2 Represents a substituent. When n is 2 or more, R A 2 Each independently represents a substituent.
A represents a single bond or a 2-valent linking group.
Z represents an atomic group which forms a monocyclic structure or a polycyclic structure together with the group represented by-O-C (=O) -O-in the formula.
The resin (A) also preferably has a repeating unit as the repeating unit X4 described in the paragraph < 0370 > < 0414 > in the specification of U.S. patent application publication 2016/007067A 1.
The resin (a) may contain 1 kind of repeating unit X4 alone or 2 or more kinds of repeating units X4 together.
Specific examples of the monomer corresponding to the repeating unit represented by the general formula (III) and specific examples of the monomer corresponding to the repeating unit represented by the general formula (A-1) are given below, but the present invention is not limited to these specific examples. The following specific examples correspond to R in the general formula (III) 7 And R in the general formula (A-1) A 1 In the case of methyl, but R 7 R is R A 1 An organic group which can be optionally substituted with a hydrogen atom, a halogen atom or a valence of 1.
[ chemical formula 13]
In addition to the above monomers, monomers shown below can also be suitably used as the raw material of the resin (a).
[ chemical formula 14]
The content of the repeating unit X4 (in the case where a plurality of repeating units X4 are present, the total thereof) contained in the resin (a) is preferably 5 to 30 mol%, more preferably 10 to 30 mol%, and even more preferably 20 to 30 mol% with respect to all the repeating units in the resin (a).
Repeating units having aromatic rings
The resin (a) preferably contains a repeating unit having an aromatic ring (hereinafter, also referred to as "repeating unit X5") other than the repeating unit X1 and the repeating unit X2.
The repeating unit X5 is preferably a repeating unit represented by the following general formula (III), for example.
[ chemical formula 15]
In the repeating unit represented by the above general formula (III), R 41 、R 42 、R 43 、X 4 、L 4 Ar and Ar 4 R in the repeating unit represented by the general formula (I) respectively exemplified in the repeating unit X2 41 、R 42 、R 43 、X 4 、L 4 Ar and Ar 4 Is the same and preferably the same.
Specific examples of the raw material monomer of the repeating unit represented by the general formula (III) include benzyl (meth) acrylate and styrene.
The resin (a) may contain 1 kind of repeating unit X5 alone or 2 or more kinds of repeating units X5 together.
In the resin (a), the content of the repeating unit X5 (in the case where a plurality of repeating units X5 are present, the total thereof) is preferably 5 mol% or more, more preferably 5 to 30 mol%, and even more preferably 5 to 20 mol% based on all the repeating units of the resin (a).
The resin (a) may have various repeating structural units for the purpose of adjusting dry etching resistance, standard developer compatibility, substrate adhesion, resist profile, general required characteristics of the resist, that is, analysis force, heat resistance, sensitivity, and the like, in addition to the repeating structural units.
Examples of such a repeating structural unit include, but are not limited to, a repeating structural unit corresponding to a predetermined monomer.
Examples of the predetermined monomer include compounds having 1 addition polymerizable unsaturated bond selected from the group consisting of acrylates, methacrylates, acrylamides, methacrylamides, allyl compounds, vinyl ethers, vinyl esters, and the like.
In addition, an addition polymerizable unsaturated compound copolymerizable with the monomer corresponding to the above-mentioned various repeating structural units may be used.
In the resin (a), the molar ratio of each repeating structural unit may be appropriately set for the purpose of adjusting various properties.
The weight average molecular weight of the resin (a) is preferably 5000 to 30000, more preferably 10000 to 25000, and even more preferably 13000 to 20000. The dispersity (Mw/Mn) is usually 1.1 to 2.2, preferably 1.1 to 2.0, more preferably 1.1 to 1.7, still more preferably 1.1 to 1.4.
The resin (A) may be used alone or in combination of 1 kind or 2 or more kinds.
In the composition of the present invention, the content of the resin (a) is usually 20 mass% or more, preferably 40 mass% or more, more preferably 60 mass% or more, and still more preferably 80 mass% or more, based on the total solid content of the composition. The upper limit is not particularly limited, but is preferably 99.5 mass% or less, more preferably 99 mass% or less, and still more preferably 98 mass% or less.
Specific additive (B) >, a process for producing the same
The composition of the present invention contains a specific additive (hereinafter, also referred to as "specific additive (B)").
With respect to the specific additive (B), the melting point or glass transition temperature is less than 25℃and the molecular weight is 180 or more. The specific additive (B) may be one having at least one of a melting point and a glass transition temperature of less than 25 ℃. By having the above-described predetermined characteristics, the plasticity of the formed resist film is improved, and as a result, for example, the solvent in the film is easily volatilized at the time of exposure Pre-Bake (PB (Pre bak)) or the like.
In terms of more excellent film density of the formed pattern, the melting point and glass transition temperature (Tg (°c)) of the specific additive (B) are preferably 25 ℃ or less, more preferably 0 ℃ or less. The lower limit is, for example, -100℃or higher. The melting point and glass transition temperature are measured by a Differential Scanning Calorimetry (DSC) method when there is a catalogue value or a literature value, and when there is no catalogue value or literature value.
In addition, the molecular weight of the specific additive (B) is preferably 200 or more in terms of more excellent film density of the formed pattern. The upper limit value is, for example, 400 or less. In addition, in the case where the specific additive (B) has a molecular weight distribution, the weight average molecular weight thereof is preferably 200 or more in terms of more excellent film density of the formed pattern. The upper limit value is, for example, 400 or less.
The specific additive (B) is not particularly limited as long as the above conditions are satisfied, and is preferably water-soluble in terms of being easily dissolved in an alkaline developer at the time of development. The term "water-soluble" means that the solubility in water (25 ℃ C.) is 300g/L or more.
When the specific additive (B) is water-soluble, it is easily dissolved in a developer during development, and therefore, it is less likely to remain in the pattern, and as a result, the film density of the formed pattern is more excellent.
Further, as the specific additive (B), among them, a reactive group having a capability of reacting with a polar group in the resin is preferable.
The reactive group is not particularly limited, and examples thereof include a hydroxyl group, a carboxyl group, an amino group, and the like. Since the specific additive (B) has the reactive group, the specific additive (B) is bonded to the resin through the reactive group and incorporated into the film after exposing and developing the resist film, and thus the film density of the formed pattern is more excellent.
Examples of the specific additive (B) include compounds having a poly (oxyalkylene) structure.
In the compound having a poly (oxyalkylene) structure, the number of carbon atoms in the oxyalkylene unit is preferably 2 to 6, more preferably 2 to 3. The average addition number of the oxyalkylene units is preferably 2 to 10, more preferably 2 to 6.
Specific additives (B) include, for example, the following additives.
[ chemical formula 16]
The specific additive (B) may be used alone or in combination of 2 or more.
In the composition of the present invention, the content of the specific additive (B) is 1 mass% or more, preferably 3 mass% or more, and more preferably 5 mass% or more, relative to the total solid content of the composition. The upper limit is, for example, 30 mass% or less, and preferably 25 mass% or less.
< photoacid generator (C) >)
The composition of the present invention comprises a photoacid generator (hereinafter also referred to as "photoacid generator (C)").
Photoacid generators are compounds that generate acid upon irradiation with actinic rays or radiation.
The photoacid generator is preferably a compound that generates an organic acid upon irradiation with actinic rays or radiation. Examples thereof include sulfonium salt compounds, iodonium salt compounds, diazonium salt compounds, phosphonium salt compounds, imide sulfonate compounds, oxime sulfonate compounds, diazonium disulfonate compounds, and o-nitrobenzyl sulfonate compounds.
As the photoacid generator, a known compound that generates an acid upon irradiation with actinic rays or radiation can be appropriately selected and used alone or in the form of a mixture of these. For example, a known compound disclosed in the specification of U.S. patent application publication 2016/007067A 1, the specification of paragraph < 0125 > - < 0319 >, the specification of U.S. patent application publication 2015/0004544A1, the specification of paragraph < 0086 > - < 0094 > and the specification of U.S. patent application publication 2016/0237190A1, the specification of paragraph < 0323 > - < 0402 > can be preferably used as the photoacid generator (C).
The photoacid generator (C) is preferably a compound represented by the following general formula (ZI), general formula (ZII) or general formula (ZIII), for example.
[ chemical formula 17]
In the above-mentioned general formula (ZI),
R 201 、R 202 r is R 203 Each independently represents an organic group.
As R 201 、R 202 R is R 203 The number of carbon atoms of the organic group is usually 1 to 30, preferably 1 to 20.
And R is 201 ～R 203 May be bonded to form a ring structure, and the ring may contain an oxygen atom, a sulfur atom, an ester bond, an amide bond, or a carbonyl group. As R 201 ～R 203 Examples of the groups formed by bonding 2 of the above groups include alkylene groups (e.g., butylene and pentylene) and-CH 2 -CH 2 -O-CH 2 -CH 2 -。
Z - Representing anions.
Preferable examples of the cation in the general formula (ZI) include the corresponding groups in the compounds (ZI-1), (ZI-2), (ZI-3) and (ZI-4) described below.
The photoacid generator (C) may be a compound having a structure represented by a plurality of general formulae (ZI). For example, it may beR of a compound represented by the general formula (ZI) 201 ～R 203 R of at least one of the compounds with another compound represented by the general formula (ZI) 201 ～R 203 A compound having a structure in which at least one of them is bonded via a single bond or a linking group.
First, the compound (ZI-1) will be described.
The compound (ZI-1) is R of the above formula (ZI) 201 ～R 203 At least one of which is an aryl sulfonium compound, that is, a compound having an aryl sulfonium as a cation.
The aryl sulfonium compound may be R 201 ～R 203 All being aryl groups, or R 201 ～R 203 Part of which is aryl and the remainder is alkyl or cycloalkyl.
Examples of the aryl sulfonium compound include triarylsulfonium compounds, diarylalkyl sulfonium compounds, aryl dialkyl sulfonium compounds, diarylcycloalkyl sulfonium compounds, and aryl dicycloalkyl sulfonium compounds.
The aryl group contained in the aryl sulfonium compound is preferably a phenyl group or a naphthyl group, and more preferably a phenyl group. The aryl group may be an aryl group having a heterocyclic structure having an oxygen atom, a nitrogen atom, a sulfur atom or the like. Examples of the heterocyclic structure include pyrrole residues, furan residues, thiophene residues, indole residues, benzofuran residues, and benzothiophene residues. When the aryl sulfonium compound has 2 or more aryl groups, the aryl groups having 2 or more aryl groups may be the same or different.
The alkyl group or cycloalkyl group of the aryl sulfonium compound is preferably a linear alkyl group having 1 to 15 carbon atoms, a branched alkyl group having 3 to 15 carbon atoms or a cycloalkyl group having 3 to 15 carbon atoms, and examples thereof include methyl, ethyl, propyl, n-butyl, sec-butyl, tert-butyl, cyclopropyl, cyclobutyl and cyclohexyl groups.
R 201 ～R 203 The aryl group, the alkyl group and the cycloalkyl group of (a) may each independently have an alkyl group (e.g., having 1 to 15 carbon atoms), a cycloalkyl group (e.g., having 3 to 15 carbon atoms), an aryl group (e.g., having 6 to 14 carbon atoms), an alkoxy group (e.g., having 1 to 15 carbon atoms), a halogen atomA child, hydroxy or phenylthio group as a substituent.
Next, the compound (ZI-2) will be described.
The compound (ZI-2) is R in the formula (ZI) 201 ～R 203 Each independently represents a compound having an organic group having no aromatic ring. Here, the aromatic ring also includes an aromatic ring containing a heteroatom.
As R 201 ～R 203 The number of carbon atoms of the organic group having no aromatic ring is usually 1 to 30, preferably 1 to 20.
R 201 ～R 203 Each independently is preferably an alkyl group, a cycloalkyl group, an allyl group or a vinyl group, more preferably a linear or branched 2-oxo-alkyl group, a 2-oxo-cycloalkyl group or an alkoxycarbonylmethyl group, and still more preferably a linear or branched 2-oxo-alkyl group.
As R 201 ～R 203 The alkyl group and the cycloalkyl group of (a) are preferably a linear alkyl group having 1 to 10 carbon atoms or a branched alkyl group having 3 to 10 carbon atoms (e.g., methyl, ethyl, propyl, butyl and pentyl) or a cycloalkyl group having 3 to 10 carbon atoms (e.g., cyclopentyl, cyclohexyl and norbornyl).
R 201 ～R 203 May be further substituted with a halogen atom, an alkoxy group (for example, having 1 to 5 carbon atoms), a hydroxyl group, a cyano group or a nitro group.
Next, the compound (ZI-3) will be described.
The compound (ZI-3) is represented by the following general formula (ZI-3) and has a benzoylmethylsulfonium salt structure.
[ chemical formula 18]
In the general formula (ZI-3),
R 1c ～R 5c each independently represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, an alkoxy group, an aryloxy group, an alkoxycarbonyl group, an alkylcarbonyloxy group, a cycloalkylcarbonyloxy group, a halogen atom, a hydroxyl group, a nitro group, an alkylthio group orArylthio.
R 6c R is R 7c Each independently represents a hydrogen atom, an alkyl group, a cycloalkyl group, a halogen atom, a cyano group, or an aryl group.
R x R is R y Each independently represents alkyl, cycloalkyl, 2-oxoalkyl, 2-oxocycloalkyl, alkoxycarbonylalkyl, allyl or vinyl.
R 1c ～R 5c More than 2 of any one of R 5c And R is R 6c 、R 6c And R is R 7c 、R 5c And R is R x R is R x And R is R y Each may be bonded to form a ring structure, which may each independently contain an oxygen atom, a sulfur atom, a ketone group, an ester bond, or an amide bond.
Examples of the ring structure include an aromatic or non-aromatic hydrocarbon ring, an aromatic or non-aromatic heterocyclic ring, and a polycyclic condensed ring formed by combining 2 or more of these rings. The ring structure may be a 3-to 10-membered ring, preferably a 4-to 8-membered ring, more preferably a 5-or 6-membered ring.
As R 1c ～R 5c More than 2 of any one of R 6c And R is R 7c R is R x And R is R y Examples of the group formed by bonding include a butylene group and a pentylene group.
As R 5c And R is R 6c R is R 5c And R is R x The group formed by bonding is preferably a single bond or an alkylene group. Examples of the alkylene group include methylene and vinyl.
Zc - Representing anions.
Next, the compound (ZI-4) will be described.
The compound (ZI-4) is represented by the following general formula (ZI-4).
[ chemical formula 19]
In the general formula (ZI-4),
l represents an integer of 0 to 2.
r represents an integer of 0 to 8.
R 13 Represents a hydrogen atom, a fluorine atom, a hydroxyl group, an alkyl group, a cycloalkyl group, an alkoxy group, an alkoxycarbonyl group, or a group having a cycloalkyl group. These groups may have a substituent.
R 14 Represents hydroxy, alkyl, cycloalkyl, alkoxy, alkoxycarbonyl, alkylcarbonyl, alkylsulfonyl, cycloalkylsulfonyl or a group having cycloalkyl. These groups may have a substituent. R is R 14 When a plurality of the above-mentioned groups are present, each independently represents a hydroxyl group or the like.
R 15 Each independently represents an alkyl group, a cycloalkyl group or a naphthyl group. These groups may have a substituent. 2R 15 Can be bonded to each other to form a ring. When 2R 15 When bonded to each other to form a ring, the ring skeleton may contain a hetero atom such as an oxygen atom or a nitrogen atom. In one embodiment, 2R 15 Is an alkylene group, and is preferably bonded to each other to form a ring structure.
Z - Representing anions.
In the general formula (ZI-4), R 13 、R 14 R is R 15 The alkyl group of (2) is linear or branched. The number of carbon atoms of the alkyl group is preferably 1 to 10. The alkyl group is more preferably a methyl group, an ethyl group, an n-butyl group, a tert-butyl group, or the like.
Next, general formulae (ZII) and (ZIII) will be described.
In the general formulae (ZII) and (ZIII), R 204 ～R 207 Each independently represents aryl, alkyl or cycloalkyl.
As R 204 ～R 207 Preferably phenyl or naphthyl, more preferably phenyl. R is R 204 ～R 207 The aryl group of (a) may be an aryl group having a heterocyclic structure having an oxygen atom, a nitrogen atom, a sulfur atom or the like. Examples of the skeleton of the aryl group having a heterocyclic structure include pyrrole, furan, thiophene, indole, benzofuran, and benzothiophene.
As R 204 ～R 207 The alkyl group and cycloalkyl group of (a) are preferably a linear alkyl group having 1 to 10 carbon atoms or a branched alkyl group having 3 to 10 carbon atoms(e.g., methyl, ethyl, propyl, butyl, and pentyl) or cycloalkyl groups having 3 to 10 carbon atoms (e.g., cyclopentyl, cyclohexyl, and norbornyl).
R 204 ～R 207 The aryl, alkyl, and cycloalkyl groups of (a) may each independently have a substituent. As R 204 ～R 207 Examples of the substituent(s) which may be present in the aryl group, the alkyl group and the cycloalkyl group include an alkyl group (for example, having 1 to 15 carbon atoms), a cycloalkyl group (for example, having 3 to 15 carbon atoms), an aryl group (for example, having 6 to 15 carbon atoms), an alkoxy group (for example, having 1 to 15 carbon atoms), a halogen atom, a hydroxyl group and a phenylthio group.
Z - Representing anions.
As Z in the general formula (ZI) - Z in the general formula (ZII) - Zc in the general formula (ZI-3) - And Z in the general formula (ZI-4) - Preferably an anion represented by the following general formula (3).
[ chemical formula 20]
In the general formula (3),
o represents an integer of 1 to 3. p represents an integer of 0 to 10. q represents an integer of 0 to 10.
Xf represents a fluorine atom or an alkyl group substituted with at least one fluorine atom. The number of carbon atoms of the alkyl group is preferably 1 to 10, more preferably 1 to 4. Further, as the alkyl group substituted with at least one fluorine atom, a perfluoroalkyl group is preferable.
Xf is preferably a fluorine atom or a perfluoroalkyl group having 1 to 4 carbon atoms, more preferably a fluorine atom or CF 3 . In particular, it is more preferred that both Xf are fluorine atoms.
R 4 R is R 5 Each independently represents a hydrogen atom, a fluorine atom, an alkyl group, or an alkyl group substituted with at least one fluorine atom. When there are a plurality of R 4 R is R 5 When R is 4 R is R 5 The two may be the same or different.
R 4 R is R 5 The alkyl group represented may have a substituent, preferablyHaving 1 to 4 carbon atoms. R is R 4 R is R 5 Preferably a hydrogen atom.
Specific examples and preferred modes of the alkyl group substituted with at least one fluorine atom are the same as those of Xf in the general formula (3).
L represents a 2-valent linking group. When a plurality of L's exist, L's may be the same or different.
As the linking group of the valence of 2, examples include-COO- (-C (=O) -O-); -OCO-, -CONH-, -NHCO-, -CO-, -O-, -S-, -SO 2 And a 2-valent linking group formed by combining a plurality of these groups, such as an alkylene group (preferably having 1 to 6 carbon atoms), a cycloalkylene group (preferably having 3 to 15 carbon atoms), and an alkenylene group (preferably having 2 to 6 carbon atoms). Among these, the number of the components is, preferably-COO-, -OCO-, -CONH-, -NHCO-, -CO-, -O-, -SO 2 -, -COO-alkylene-, -OCO-alkylene-, -CONH-alkylene-or-NHCO-alkylene-, more preferably-COO-, -OCO-, -CONH-, -SO 2 -, -COO-alkylene-or-OCO-alkylene-.
W represents an organic group containing a cyclic structure. Among these, a cyclic organic group is preferable.
Examples of the cyclic organic group include alicyclic groups, aryl groups, and heterocyclic groups.
The alicyclic group may be a monocyclic group or a polycyclic group. Examples of the monocyclic alicyclic group include monocyclic cycloalkyl groups such as cyclopentyl, cyclohexyl, and cyclooctyl. Examples of the polycyclic alicyclic group include polycyclic cycloalkyl groups such as norbornyl, tricyclodecyl, tetracyclodecyl, tetracyclododecyl, and adamantyl. Among them, alicyclic groups having a high-volume structure and having 7 or more carbon atoms such as norbornyl, tricyclodecyl, tetracyclodecyl, tetracyclododecyl and adamantyl are preferable.
The aryl group may be monocyclic or polycyclic. Examples of the aryl group include phenyl, naphthyl, phenanthryl and anthracyl.
The heterocyclic group may be a monocyclic group or a polycyclic group. The polycyclic ring more inhibits diffusion of acid. The heterocyclic group may or may not have aromatic properties. Examples of the heterocyclic ring having an aromatic property include a furan ring, a thiophene ring, a benzofuran ring, a benzothiophene ring, a dibenzofuran ring, a dibenzothiophene ring, and a pyridine ring. Examples of the heterocyclic ring having no aromatic property include a tetrahydropyran ring, a lactone ring, a sultone ring, and a decahydroisoquinoline ring. Examples of the lactone ring and the sultone ring include the lactone structures and sultone structures shown in the resins described above. The heterocyclic ring in the heterocyclic group is particularly preferably a furan ring, a thiophene ring, a pyridine ring or a decahydroisoquinoline ring.
The cyclic organic group may have a substituent. Examples of the substituent include an alkyl group (which may be any of a straight chain and a branched chain, and preferably has 1 to 12 carbon atoms), a cycloalkyl group (which may be any of a monocyclic ring, a polycyclic ring, and a spiro ring, and preferably has 3 to 20 carbon atoms), an aryl group (which may be any of a 6 to 14 carbon atoms), a hydroxyl group, an alkoxy group, an ester group, an amide group, a carbamate group, a urea group, a thioether group, a sulfonamide group, and a sulfonate group. In addition, the carbon constituting the cyclic organic group (carbon contributing to the formation of a ring) may be a carbonyl carbon.
As the anion represented by the general formula (3), SO is preferable 3 - -CF 2 -CH 2 -OCO-(L)q’-W、SO 3 - -CF 2 -CHF-CH 2 -OCO-(L)q’-W、SO 3 - -CF 2 -COO-(L)q’-W、SO 3 - -CF 2 -CF 2 -CH 2 -CH 2 - (L) q-W or SO 3 - -CF 2 -CH(CF 3 ) -OCO- (L) q' -W. Wherein L, q and W are the same as in formula (3). q' represents an integer of 0 to 10.
In one embodiment, Z is represented by the general formula (ZI) - Z in the general formula (ZII) - Zc in the general formula (ZI-3) - And Z in the general formula (ZI-4) - Anions represented by the following general formula (4) are also preferred.
[ chemical formula 21]
In the general formula (4),
X B1 x is X B2 Each independently represents a hydrogen atom or a 1-valent organic group having no fluorine atom. X is X B1 X is X B2 Preferably a hydrogen atom.
X B3 X is X B4 Each independently represents a hydrogen atom or a 1-valent organic group. Preferably X B3 X is X B4 At least one of them is a fluorine atom or an organic group having a valence of 1, more preferably X B3 X is X B4 Both are fluorine atoms or 1-valent organic groups having fluorine atoms. More preferably X B3 X is X B4 Both are alkyl groups substituted with fluorine atoms.
L, q and W are the same as those of the general formula (3).
Z in the general formula (ZI) - Z in the general formula (ZII) - Zc in the general formula (ZI-3) - And Z in the general formula (ZI-4) - May be a benzenesulfonic acid anion, preferably a benzenesulfonic acid anion substituted with branched alkyl or cycloalkyl groups.
As Z in the general formula (ZI) - Z in the general formula (ZII) - Zc in the general formula (ZI-3) - And Z in the general formula (ZI-4) - Also preferred is an aromatic sulfonic acid anion represented by the following general formula (SA 1).
[ chemical formula 22]
In the formula (SA 1), the amino acid sequence,
ar represents an aryl group, and may further have a substituent other than a sulfonic acid anion and a- (D-B) group. Examples of the substituent that may be further contained include a fluorine atom, a hydroxyl group, and the like.
n represents an integer of 0 or more. N is preferably 1 to 4, more preferably 2 to 3, and still more preferably 3.
D represents a single bond or a 2-valent linking group. Examples of the 2-valent linking group include an ether group, a thioether group, a carbonyl group, a sulfoxide group, a sulfone group, a sulfonate group, an ester group, and a group containing a combination of 2 or more of these groups.
B represents a hydrocarbon group.
Preferably, D is a single bond and B is an aliphatic hydrocarbon structure. B is more preferably isopropyl or cyclohexyl.
Preferred examples of the sulfonium cation of the general formula (ZI) and the iodonium cation of the general formula (ZII) are shown below.
[ chemical formula 23]
The anions Z of the general formula (ZI) and the general formula (ZII) are shown below - Zc in the general formula (ZI-3) - And Z in the general formula (ZI-4) - Is a preferred example of (a).
[ chemical formula 24]
Any combination of the above cations and anions can be used as the photoacid generator.
The photoacid generator may be in the form of a low molecular compound or incorporated into a part of the polymer. In addition, the form of the low-molecular compound and the form incorporated in a part of the polymer may be used together.
The photoacid generator is preferably in the form of a low molecular compound.
When the photoacid generator is in the form of a low molecular compound, the molecular weight is preferably 3,000 or less, more preferably 2,000 or less, and further preferably 1,000 or less.
When the photoacid generator is incorporated into a part of the polymer, it may be incorporated into a part of the aforementioned resin (a) or into a resin different from the resin (a).
The photoacid generator may be used alone or in combination of 1 or more than 2.
In the composition of the present invention, the content of the photoacid generator (in the case where a plurality of photoacid generators are present, the total amount thereof) is preferably 0.1 to 35% by mass, more preferably 0.5 to 25% by mass, still more preferably 1 to 20% by mass, and particularly preferably 1 to 15% by mass, relative to the total solid content of the composition.
< acid diffusion controlling agent (D) >)
The composition of the present invention preferably comprises an acid diffusion controlling agent (D).
The acid diffusion controller (D) functions as a quencher (sequencer) that captures an acid generated from a photoacid generator or the like at the time of exposure and suppresses the reaction of the acid-decomposable resin in the unexposed portion caused by the excessive acid generation. For example, an alkali compound (DA), an alkali compound (DB) whose alkali is reduced or eliminated by irradiation with actinic rays or radiation, an onium salt (DC) which is a relatively weak acid with respect to an acid generator, a low molecular compound (DD) having a nitrogen atom and having a group which is detached by the action of an acid, an onium salt compound (DE) having a nitrogen atom in a cation portion, or the like can be used as the acid diffusion controlling agent. In the composition of the present invention, a known acid diffusion controlling agent can be preferably used. For example, a known compound disclosed in the specification of U.S. patent application publication 2016/007067A 1, paragraph < 0627 > - < 0664 >, the specification of U.S. patent application publication 2015/0004544A1, paragraph < 0095 > - < 0187 >, the specification of U.S. patent application publication 2016/0237190A1, paragraph < 0403 > - < 0423 >, and the specification of U.S. patent application publication 2016/0274458A1, paragraph < 0259 > - < 0328, can be preferably used as the acid diffusion controlling agent (D).
The basic compound (DA) is preferably a compound having a structure represented by the following formulas (a) to (E).
[ chemical formula 25]
In the general formula (A) and (E),
R 200 、R 201 r is R 202 May be the same or different and each independently represents a hydrogen atom, an alkyl group (preferably having 1 to 20 carbon atoms), a cycloalkyl group (preferably having 3 to 20 carbon atoms), or an aryl group (having 6 to 20 carbon atoms) R 201 And R is R 202 Can be bonded to each other to form a ring.
R 203 、R 204 、R 205 R is R 206 May be the same or different and each independently represents an alkyl group having 1 to 20 carbon atoms.
The alkyl groups in the general formulae (A) and (E) may have a substituent or may be unsubstituted.
The alkyl group is preferably an aminoalkyl group having 1 to 20 carbon atoms, a hydroxyalkyl group having 1 to 20 carbon atoms, or a cyanoalkyl group having 1 to 20 carbon atoms.
The alkyl groups in the general formulae (A) and (E) are more preferably unsubstituted.
The basic compound (DA) is preferably guanidine, aminopyrrolidine, pyrazole, pyrazoline, piperazine, aminomorpholine, aminoalkylmorpholine, piperidine or the like, and more preferably a compound having an imidazole structure, diazabicyclo structure, onium hydroxide structure, onium carboxylate structure, trialkylamine structure, aniline structure or pyridine structure, an alkylamine derivative having a hydroxyl group and/or an ether bond, an aniline derivative having a hydroxyl group and/or an ether bond or the like.
An alkaline compound (DB) (hereinafter also referred to as "compound (DB)") having a proton acceptor functional group and having a proton acceptor property reduced, disappeared or changed from proton acceptor to acid by irradiation of actinic rays or radiation.
The proton acceptor functional group is a functional group having a group or an electron capable of electrostatically interacting with a proton, and for example, represents a functional group having a macrocyclic structure such as a cyclic polyether or a functional group containing a nitrogen atom having an unshared electron pair that does not contribute to pi conjugation. The nitrogen atom having an unshared electron pair that does not contribute to pi conjugation refers to, for example, a nitrogen atom having a partial structure represented by the following formula.
[ chemical formula 26]
UnsharedElectron pair
Examples of the preferable partial structure of the proton acceptor functional group include a crown ether structure, an aza crown ether structure, a primary to tertiary amine structure, a pyridine structure, an imidazole structure, and a pyrazine structure.
The compound (DB) generates a compound which undergoes degradation by irradiation with actinic rays or radiation to reduce or eliminate proton acceptors or changes from proton acceptors to acidity. The decrease or disappearance of proton acceptors or change from proton acceptors to acidity refers to change in proton acceptors caused by addition of protons to proton acceptors, specifically, decrease in equilibrium constant in chemical equilibrium when proton adducts are formed from a compound (DB) having proton acceptors and protons.
Proton acceptors can be confirmed by performing pH measurements.
The acid dissociation constant pKa of the compound produced by decomposition of the compound (DB) by irradiation with actinic rays or radiation is preferably pKa < 1, more preferably-13 < pKa < 1, still more preferably-13 < pKa < 3.
The acid dissociation constant pKa represents the acid dissociation constant pKa in aqueous solution, and is defined, for example, in chemical toilet seat (II) (revised version 4, 1993, japanese chemical society, maruzen Company, limited). The lower the value of the acid dissociation constant pKa, the greater the acid strength. Specifically, the acid dissociation constant pKa in an aqueous solution can be measured by measuring the acid dissociation constant at 25 ℃ using an infinitely diluted aqueous solution. Alternatively, the values of a database based on the Hammett substituent constant and the known literature values can be calculated using the software suite 1 described below. All pKa values described in the present specification represent values calculated by using the software suite.
Software suite 1: advanced Chemistry Development (ACD/Labs) Software V8.14 for Solaris (1994-2007 ACD/Labs).
In the composition of the present invention, an onium salt (DC) which is a relatively weak acid with respect to the photoacid generator can be used as an acid diffusion control agent.
When a photoacid generator and an onium salt that generates an acid that is a relatively weak acid with respect to the acid generated by the photoacid generator are used in combination, if the acid generated by the photoacid generator collides with the onium salt having an unreacted weak acid anion by irradiation of actinic rays or radiation, the weak acid is released by salt exchange to generate the onium salt having a strong acid anion. In this process, since the strong acid is replaced with a weak acid having a low catalyst ability, it is apparent that the acid is deactivated and the acid diffusion is controlled.
As the onium salt which becomes a relatively weak acid with respect to the photoacid generator, compounds represented by the following general formulae (d 1-1) to (d 1-3) are preferable.
[ chemical formula 27]
Wherein R is 51 Is hydrocarbon group which may have substituent(s), Z 2c Is a hydrocarbon group having 1 to 30 carbon atoms which may have a substituent (wherein, the carbon adjacent to S is unsubstituted with a fluorine atom), R 52 Is an organic group, Y 3 Is a linear, branched or cyclic alkylene or arylene group, rf is a hydrocarbon group containing a fluorine atom, M + Each independently is an ammonium cation, a sulfonium cation, or an iodide cation.
As denoted by M + Preferred examples of the sulfonium cation or the iodonium cation include sulfonium cations exemplified by the general formula (ZI) and iodonium cations exemplified by the general formula (ZII).
The onium salt (DC) which is a relatively weak acid with respect to the photoacid generator may be a compound (hereinafter, also referred to as "compound (DCA)") having a cation site and an anion site in the same molecule and the cation site and the anion site being linked by a covalent bond.
As the compound (DCA), compounds represented by any one of the following general formulae (C-1) to (C-3) are preferable.
[ chemical formula 28]
In the general formulae (C-1) to (C-3),
R 1 、R 2 r is R 3 Each independently represents a substituent having 1 or more carbon atoms.
L 1 Represents a 2-valent linking group or a single bond linking a cation site and an anion site.
-X - Represents a group selected from-COO - 、-SO 3 - 、-SO 2 - -N - -R 4 An anionic site in (a). R is R 4 Represents a carbonyl group (-C (=O) -) and a sulfonyl group (-S (=O)) at a connecting position with an adjacent N atom 2 A substituent of 1 valence of at least one of (-) and sulfinyl (-S (=o) -).
R 1 、R 2 、R 3 、R 4 L and L 1 Can be bonded to each other to form a ring structure. In the general formula (C-3), R is 1 ～R 3 Together, the 2 groups of (a) represent 1 substituent(s) of valence (2), which may be bonded to the N atom through a double bond.
As R 1 ～R 3 Examples of the substituent having 1 or more carbon atoms include an alkyl group, a cycloalkyl group, an aryl group, an alkoxycarbonyl group, a cycloalkoxycarbonyl group, an aryloxycarbonyl group, an alkylaminocarbonyl group, a cycloalkylaminocarbonyl group, an arylaminocarbonyl group and the like. Preferably alkyl, cycloalkyl or aryl.
L as a 2-valent linking group 1 Examples of the group include a linear or branched alkylene group, a cycloalkylene group, an arylene group, a carbonyl group, an ether bond, an ester bond, an amide bond, a urethane bond, and a urea bond, and a group formed by combining 2 or more of these. As L 1 The group is preferably an alkylene group, an arylene group, an ether bond, an ester bond, or a combination of 2 or more of them.
The low molecular compound (DD) having a nitrogen atom and having a group that is detached by the action of an acid (hereinafter, also referred to as "compound (DD)") is preferably an amine derivative having a group that is detached by the action of an acid on a nitrogen atom.
The group to be released by the action of an acid is preferably an acetal group, a carbonate group, a urethane group, a tertiary ester group, a tertiary hydroxyl group or a semiamine acetal ether group, and more preferably a urethane group or a semiamine acetal ether group.
The molecular weight of the compound (DD) is preferably 100 to 1000, more preferably 100 to 700, and still more preferably 100 to 500.
The compound (DD) may have a urethane group having a protecting group on a nitrogen atom. The protecting group constituting the urethane group is represented by the following general formula (d-1).
[ chemical formula 29]
In the general formula (d-1),
R b Each independently represents a hydrogen atom, an alkyl group (preferably having 1 to 10 carbon atoms), a cycloalkyl group (preferably having 3 to 30 carbon atoms), an aryl group (preferably having 3 to 30 carbon atoms), an aralkyl group (preferably having 1 to 10 carbon atoms), or an alkoxyalkyl group (preferably having 1 to 10 carbon atoms). R is R b Or may be connected to each other to form a ring.
R b The alkyl group, cycloalkyl group, aryl group, and aralkyl group represented may each be independently substituted with a functional group such as a hydroxyl group, cyano group, amino group, pyrrolidinyl group, piperidinyl group, morpholinyl group, oxo group, or the like, an alkoxy group, or a halogen atom. With respect to R b The same applies to the alkoxyalkyl groups represented.
As R b The alkyl group is preferably a linear or branched alkyl group, cycloalkyl group or aryl group, and more preferably a linear or branched alkyl group or cycloalkyl group.
As 2R b Examples of the ring formed by the connection include alicyclic hydrocarbon groups, aromatic hydrocarbon groups, heterocyclic hydrocarbon groups, and derivatives thereof.
Specific examples of the structure of the group represented by the general formula (d-1) include, but are not limited to, the structure disclosed in the < 0466 > section of U.S. Pat. No. 2012/0135348A 1.
The compound (DD) preferably has a structure represented by the following general formula (6).
[ chemical formula 30]
In the general formula (6),
l represents an integer of 0 to 2, m represents an integer of 1 to 3, and l+m=3 is satisfied.
R a Represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group or an aralkyl group. When l is 2, 2R a May be the same or different, 2R a Can be linked to each other to form a heterocyclic ring together with the nitrogen atom in the formula. The heterocyclic ring may contain heteroatoms other than nitrogen atoms in the formula.
R b Has the meaning as defined for R in the above formula (d-1) b The same applies to the preferred examples.
In the general formula (6), R is a The alkyl, cycloalkyl, aryl, aralkyl groups of (a) may each independently be substituted with the same group as that described above as the group which may be substituted with R b Alkyl, cycloalkyl, aryl, aralkyl.
As R as above a Specific examples of the alkyl, cycloalkyl, aryl and aralkyl groups (these groups may be substituted with the above groups) include R b The same groups as those in the above specific examples were carried out.
Specific examples of the particularly preferred compound (DD) in the present invention include, but are not limited to, the compounds disclosed in the < 0475 > section of U.S. patent application publication 2012/0135348A 1.
The onium salt compound (DE) having a nitrogen atom in the cation portion (hereinafter, also referred to as "compound (DE)") is preferably a compound having a basic portion containing a nitrogen atom in the cation portion. The basic moiety is preferably an amine group, more preferably an aliphatic amine group. All of the atoms adjacent to the nitrogen atom in the basic moiety are preferably hydrogen atoms or carbon atoms. Further, from the viewpoint of increasing the basicity, it is preferable that the electron withdrawing functional group (carbonyl group, sulfonyl group, cyano group, halogen atom, etc.) is not directly linked to the nitrogen atom.
As a preferable specific example of the compound (DE), there may be mentioned the compound disclosed in the < 0203 > paragraph of U.S. patent application publication 2015/0309408A1, but not limited thereto.
Preferred examples of the acid diffusion controlling agent (D) are shown below.
[ chemical formula 31]
[ chemical formula 32]
In the composition of the present invention, 1 or 2 or more acid diffusion controlling agents (D) may be used singly or in combination.
The content (in the case where there are plural kinds, the total amount thereof) of the acid diffusion controlling agent (D) in the composition is preferably 0.01 to 10% by mass, more preferably 0.01 to 5% by mass, relative to the total solid content of the composition.
Solvent (E) >, solvent (E)
The composition of the present invention preferably comprises a solvent.
In the composition of the present invention, a known resist solvent can be preferably used. For example, known solvents disclosed in the specification of U.S. patent application publication 2016/007067A 1, the specification of U.S. patent application publication 2015/0004544A1, the specification of U.S. patent application publication 0210, the specification of U.S. patent application publication 2016/0237190A1, the specification of U.S. patent application publication 0424, the specification of U.S. patent application publication 0426, and the specification of U.S. patent application publication 2016/0274458A1, the specification of U.S. patent application publication 0357, the specification of U.S. patent application publication 0366, can be preferably used.
Examples of the solvent that can be used in the preparation of the composition include organic solvents such as alkylene glycol monoalkyl ether carboxylate, alkylene glycol monoalkyl ether, alkyl lactate, alkyl alkoxypropionate, cyclic lactone (preferably having 4 to 10 carbon atoms), a cyclic mono-ketone compound (preferably having 4 to 10 carbon atoms), alkylene carbonate, alkyl alkoxyacetate, and alkyl pyruvate.
As the organic solvent, a mixed solvent in which a solvent containing a hydroxyl group in the structure and a solvent not containing a hydroxyl group are mixed can be used.
The above exemplified compounds can be appropriately selected as the solvent containing a hydroxyl group and the solvent not containing a hydroxyl group, and the solvent containing a hydroxyl group is preferably alkylene glycol monoalkyl ether or alkyl lactate, and more preferably Propylene Glycol Monomethyl Ether (PGME), propylene glycol monoethyl ether (PGEE), methyl 2-hydroxyisobutyrate or ethyl lactate. Further, as the solvent not containing a hydroxyl group, alkylene glycol monoalkyl ether acetate, alkyl alkoxy propionate, a mono-ketone compound which may have a ring, cyclic lactone, alkyl acetate, or the like is preferable, among these, propylene Glycol Monomethyl Ether Acetate (PGMEA), ethyl ethoxypropionate, 2-heptanone, γ -butyrolactone, cyclohexanone, cyclopentanone, or butyl acetate is more preferable, and propylene glycol monomethyl ether acetate, γ -butyrolactone, ethyl ethoxypropionate, cyclohexanone, cyclopentanone, or 2-heptanone is more preferable. Propylene carbonate is also preferred as a solvent containing no hydroxyl group.
The mixing ratio (mass ratio) of the solvent containing hydroxyl groups to the solvent not containing hydroxyl groups is 1/99 to 99/1, preferably 10/90 to 90/10, more preferably 20/80 to 60/40. In terms of coating uniformity, a mixed solvent containing 50 mass% or more of a solvent having no hydroxyl group is preferable.
The solvent is preferably a solvent containing propylene glycol monomethyl ether acetate, and may be a single solvent of propylene glycol monomethyl ether acetate or a mixed solvent of 2 or more solvents containing propylene glycol monomethyl ether acetate.
Cross-linker (F) >, and
the composition of the present invention may contain a compound that crosslinks the resin by the action of an acid (hereinafter, also referred to as "crosslinker (F)"). As the crosslinking agent (F), a known compound can be suitably used. For example, a known compound disclosed in paragraphs < 0379 > - < 0431 > of the specification of U.S. patent application publication 2016/0147154A1 and in paragraphs < 0064 > - < 0141 > of the specification of U.S. patent application publication 2016/0282720A1 can be preferably used as the crosslinking agent (F).
The crosslinking agent (F) is a compound having a crosslinkable group capable of crosslinking the resin, and examples of the crosslinkable group include a hydroxymethyl group, an alkoxymethyl group, an acyloxymethyl group, an alkoxymethyl ether group, an oxirane ring, an oxetane ring, and the like.
The crosslinkable group is preferably a hydroxymethyl group, an alkoxymethyl group, an oxirane ring or an oxetane ring.
The crosslinking agent (F) is preferably a compound (also including a resin) having 2 or more crosslinkable groups.
The crosslinking agent (F) is more preferably a phenol derivative having a hydroxymethyl group or an alkoxymethyl group, a urea compound (a compound having a urea structure), or a melamine compound (a compound having a melamine structure).
The crosslinking agent may be used alone or in combination of 1 or more than 2.
The content of the crosslinking agent (F) is preferably 1 to 50% by mass, more preferably 3 to 40% by mass, and even more preferably 5 to 30% by mass, relative to the total solid content of the resist composition.
Surfactant (G) >)
The compositions of the present invention preferably comprise a surfactant. When the surfactant is contained, a fluorine-based and/or silicon-based surfactant (specifically, a fluorine-based surfactant, a silicon-based surfactant, or a surfactant having both a fluorine atom and a silicon atom) is preferable.
The composition of the present invention contains a surfactant, and thus, when an exposure light source of 250nm or less, particularly 220nm or less is used, a pattern having excellent sensitivity and resolution and less defects in development can be obtained.
Examples of the fluorine-based and/or silicon-based surfactant include surfactants described in paragraph < 0276 > of U.S. patent application publication No. 2008/024825.
Further, surfactants other than the fluorine-based and/or silicon-based surfactants described in the paragraph < 0280 > of U.S. patent application publication No. 2008/0248225 may be used.
These surfactants may be used singly or in combination of 1 or more than 2.
When the composition of the present invention contains a surfactant, the content of the surfactant is preferably 0.0001 to 2% by mass, more preferably 0.0005 to 1% by mass, based on the total solid content of the composition.
(other additives)
The composition of the present invention may further comprise an acid-proliferating agent, a dye, a plasticizer, a photosensitizer, a light absorber, an alkali-soluble resin, a dissolution inhibitor, a dissolution accelerator, and the like.
< preparation method >)
The solid content concentration of the composition of the present invention is usually 1.0 mass% or more, and is preferably 10 mass% or more, more preferably 20 mass%, and even more preferably 30 mass% in terms of enabling formation of a thicker film pattern. The upper limit thereof is not particularly limited, and is, for example, 50 mass% or less. The solid content concentration is the mass percentage of the resist component other than the solvent with respect to the total mass of the composition.
The composition of the present invention is used by dissolving the above components in a predetermined organic solvent (preferably, the above mixed solvent), filtering the solution with a filter, and applying the solution to a predetermined support (substrate). The pore size of the filter used for the filtration is preferably 0.1 μm or less, more preferably 0.05 μm or less, and still more preferably 0.03 μm or less. The filter is preferably a polytetrafluoroethylene filter, a polyethylene filter, or a nylon filter. In the filter filtration, for example, as disclosed in japanese patent application laid-open No. 2002-062667 (japanese patent application laid-open No. 2002-062667), cyclic filtration may be performed, or filtration may be performed by connecting a plurality of filters in series or in parallel. Also, the composition may be filtered multiple times. In addition, the composition may be subjected to degassing treatment or the like before and after filtration by a filter.
The viscosity of the composition of the present invention is preferably 100 to 500 mPas. From the viewpoint of further excellent coatability, the viscosity of the composition of the present invention is more preferably 100 to 300mpa·s.
In addition, the viscosity can be measured by an E-type viscometer.
The film thickness of the resist film (in other words, the film of the actinic ray-sensitive or radiation-sensitive resin composition) composed of the composition of the present invention is, for example, 2 μm or more, more preferably 5 μm or more, and still more preferably 7 μm or more, in terms of being able to further suppress ion leakage in the ion implantation step. The upper limit is not particularly limited, and is, for example, 15 μm or less.
In addition, as described later, a pattern can be formed from the composition of the present invention.
The film thickness of the formed pattern is, for example, 2 μm or more, and more preferably 5 μm or more, and even more preferably 7 μm or more, in order to further suppress ion leakage in the ion implantation step. The upper limit is not particularly limited, and is, for example, 15 μm or less.
In addition, in order to further suppress ion leakage in the ion implantation step, the film density of the formed pattern is preferably 1.05g/cm 3 The above is more preferably 1.10g/cm 3 The above.
The film density is a film density of a film having a film thickness of 9 μm obtained by applying the composition of the present invention to a substrate to form a coating film, and then baking the coating film at 150℃for 90 seconds.
< usage >
The present invention relates to a actinic-ray-or radiation-sensitive resin composition having properties that change upon reaction by irradiation with actinic rays or radiation. More specifically, the present invention relates to a actinic radiation-sensitive or radiation-sensitive resin composition used in a process for producing a semiconductor such as an IC (Integrated Circuit), a circuit board such as a liquid crystal or thermal head (thermal head), a mold structure for imprinting, another process for photolithography, or a process for producing a lithographic plate or an acid-curable composition. The pattern formed in the present invention can be used in an ion implantation step, an etching step, a bump electrode forming step, a rewiring forming step, MEMS (Micro Electro Mechanical Systems: microelectromechanical system), and the like.
Among them, the composition of the present invention is preferably used in an ion implantation step for forming a light receiving section for an infrared ray transmitting filter (in other words, a light receiving section for sensing infrared rays) in the case of manufacturing a solid-state imaging element including the infrared ray transmitting filter which selectively transmits an infrared ray component.
[ Pattern Forming method ]
The present invention also relates to a pattern forming method using the above-mentioned actinic-ray-or radiation-sensitive resin composition. The pattern forming method of the present invention will be described below. The resist film of the present invention (in other words, the film of the actinic ray-sensitive or radiation-sensitive resin composition) will be described together with the description of the pattern forming method.
The pattern forming method of the present invention comprises the steps of:
(i) A step of forming a resist film on a support using the actinic-ray-sensitive or radiation-sensitive resin composition (resist film forming step),
(ii) A step (exposure step) of exposing the resist film to actinic rays or radiation
(iii) And developing the exposed resist film with a developer (developing step).
The pattern forming method of the present invention is not particularly limited as long as it includes the steps (i) to (iii) described above, and may further include the following steps.
In the pattern forming method of the present invention, the exposure method in the (ii) exposure step may be immersion exposure.
In the pattern forming method of the present invention, it is preferable that the step (iv) of preheating (PB: preBake) is included before the step (ii) of exposing.
In the pattern forming method of the present invention, it is preferable that the method further includes (v) a post exposure heating (PEB: postexposure baking) step after the (ii) exposure step and before the (iii) development step.
In the pattern forming method of the present invention, the exposure step (ii) may be included a plurality of times.
In the pattern forming method of the present invention, the preheating step (iv) may be included a plurality of times.
The pattern forming method of the present invention may include a plurality of (v) post-exposure heating steps.
In the pattern forming method of the present invention, the (i) film forming step, (ii) exposure step, and (iii) developing step can be performed by a generally known method.
Further, a resist underlayer film (for example, SOG (Spin On Glass), SOC (Spin On Carbon), and antireflection film) may be formed between the resist film and the support as needed. As a material constituting the resist underlayer film, a known organic or inorganic material can be suitably used.
A protective film (top coat layer) may be formed on the upper layer of the resist film. As the protective film, a known material can be used as appropriate. For example, a protective film-forming composition disclosed in U.S. patent application publication No. 2007/0178407, U.S. patent application publication No. 2008/0085466, U.S. patent application publication No. 2007/0275326, U.S. patent application publication No. 2016/0299432, U.S. patent application publication No. 2013/024438, and international patent application publication No. 2016/157988A can be preferably used. The composition for forming a protective film is preferably a composition containing the acid diffusion controlling agent.
The support is not particularly limited, and a substrate commonly used in a photolithography process or the like of a photosensitive etching process other than a process for manufacturing a semiconductor such as an IC or a process for manufacturing a circuit substrate such as a liquid crystal or a thermal head (thermal head) can be used. Specific examples of the support include silicon and SiO 2 An inorganic substrate such as SiN, etc.
The baking temperature is preferably 70 to 130℃and more preferably 80 to 120℃in either of the (iv) pre-baking step and the (v) post-exposure baking step.
The heating time is preferably 30 to 300 seconds, more preferably 30 to 180 seconds, and even more preferably 30 to 90 seconds in either of the preheating step (iv) and the post-exposure heating step (v).
Heating can be performed by a mechanism provided in the exposure apparatus and the developing apparatus, or by using a heating plate or the like.
The wavelength of the light source used in the exposure step is not limited, and examples thereof include infrared light, visible light, ultraviolet light, extreme ultraviolet light (EUV), X-rays, and electron beams. Among these, far ultraviolet light is preferable, and the wavelength thereof is preferably 250nm or less, more preferably 220nm or less, and further preferably 1 to 200nm. Specifically, krF excimer laser (248 nm), arF excimer laser (193 nm), F 2 Excimer laser (157 nm), X-ray, EUV (13 nm), electron beam, and the like are preferable, and KrF excimer laser, arF excimer laser, EUV, or electron beam is more preferable.
(iii) The developer used in the developing step may be an alkaline developer or a developer containing an organic solvent (hereinafter, also referred to as an "organic-based developer").
As the alkali developer, a quaternary ammonium salt typified by tetramethylammonium hydroxide is generally used, and in addition to this, an aqueous alkali solution of an inorganic base, primary to tertiary amines, alcohol amines, cyclic amines, or the like can be used.
The alkaline developer may further contain an appropriate amount of an alcohol and/or a surfactant. The alkali concentration of the alkali developer is usually 0.1 to 20 mass%. The pH of the alkaline developer is typically 10 to 15.
The time for development using an alkaline developer is usually 10 to 300 seconds.
The alkali concentration, pH and development time of the alkaline developer can be appropriately adjusted according to the pattern to be formed.
The organic developer is preferably a developer containing at least 1 organic solvent selected from the group consisting of ketone solvents, ester solvents, alcohol solvents, amide solvents, ether solvents, and hydrocarbon solvents.
Examples of the ketone solvent include 1-octanone, 2-octanone, 1-nonanone, 2-nonanone, acetone, 2-heptanone (methylpentyl ketone), 4-heptanone, 1-hexanone, 2-hexanone, diisobutyl ketone, cyclohexanone, methylcyclohexanone, phenylpropione, methylethyl ketone, methylisobutylketone, acetylacetone, acetonylacetone, ionone, diacetone alcohol, acetonyl alcohol, acetophenone, methylnaphthyl ketone, isophorone, and propylene carbonate.
Examples of the ester solvents include methyl acetate, butyl acetate, ethyl acetate, isopropyl acetate, amyl acetate (amyl acetate), isoamyl acetate, amyl acetate (amyl acetate), propylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, diethylene glycol monoethyl ether acetate, ethyl-3-ethoxypropionate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, methyl formate, ethyl formate, butyl formate, propyl formate, ethyl lactate, butyl lactate, propyl lactate, butyl butyrate, methyl 2-hydroxyisobutyrate, isoamyl acetate, isobutyl isobutyrate, and butyl propionate.
As the alcohol-based solvent, amide-based solvent, ether-based solvent and hydrocarbon-based solvent, the solvents disclosed in the paragraphs < 0715 > - < 0718 > of the specification of U.S. patent application publication 2016/007067A 1 can be used.
The above-mentioned solvents may be mixed in plural, or may be mixed with solvents other than the above-mentioned solvents or water. The water content of the entire developer is preferably less than 50% by mass, more preferably less than 20% by mass, still more preferably less than 10% by mass, and particularly preferably contains substantially no water.
The content of the organic solvent relative to the total amount of the organic developer is preferably 50 to 100% by mass, more preferably 80 to 100% by mass, still more preferably 90 to 100% by mass, and particularly preferably 95 to 100% by mass.
The organic developer may contain a known surfactant in an appropriate amount as required.
The content of the surfactant is usually 0.001 to 5% by mass, preferably 0.005 to 2% by mass, and 0.01 to 0.5% by mass based on the total amount of the developer.
The organic-based developer may contain the acid diffusion controlling agent.
Examples of the developing method include: a method of immersing the substrate in a tank filled with a developer for a certain period of time (immersion method); a method of depositing a developer on the surface of the substrate by surface tension and standing for a certain period of time (spin-on immersion method); a method of spraying a developer solution onto a surface of a substrate (spraying method); or a method of continuously discharging the developer while scanning the developer discharge nozzle at a constant speed on a substrate rotated at a constant speed (dynamic dispensing method); etc.
The step of developing with an aqueous alkali solution (alkaline developing step) and the step of developing with a developer containing an organic solvent (organic solvent developing step) may be combined. Thus, since the pattern can be formed in a state where only the region of the intermediate exposure intensity is not dissolved, a finer pattern can be formed.
Preferably, the developing step (iii) is followed by a step of washing with a rinse solution (rinsing step).
The rinse liquid used in the rinse step after the development step using the alkaline developer can be, for example, pure water. The pure water may contain an appropriate amount of surfactant. In this case, a treatment of removing the developing solution or the rinse solution adhering to the pattern by the supercritical fluid may be added after the developing step or the rinsing step. In addition, after the rinsing treatment or the treatment with the supercritical fluid, a heating treatment may be performed to remove moisture remaining in the pattern.
The rinse solution used in the rinse step after the development step using the developer containing an organic solvent is not particularly limited as long as the pattern is not dissolved, and a solution containing a normal organic solvent can be used. As the rinse liquid, a rinse liquid containing at least 1 organic solvent selected from the group consisting of hydrocarbon solvents, ketone solvents, ester solvents, alcohol solvents, amide solvents, and ether solvents is preferably used.
Specific examples of the hydrocarbon-based solvent, ketone-based solvent, ester-based solvent, alcohol-based solvent, amide-based solvent, and ether-based solvent include the same solvents as those described in the developer containing an organic solvent.
The rinse solution used in the rinsing step at this time is more preferably a rinse solution containing 1-polyol.
As the 1-polyol used in the washing step, there may be mentioned linear, branched or cyclic 1-polyol. Specifically, 1-butanol, 2-butanol, 3-methyl-1-butanol, third butanol, 1-pentanol, 2-pentanol, 1-hexanol, 4-methyl-2-pentanol, 1-heptanol, 1-octanol, 2-hexanol, cyclopentanol, 2-heptanol, 2-octanol, 3-hexanol, 3-heptanol, 3-octanol, 4-octanol, and methyl isobutyl carbinol may be cited. Examples of the 1-polyol having 5 or more carbon atoms include 1-hexanol, 2-hexanol, 4-methyl-2-pentanol, 1-pentanol, 3-methyl-1-butanol, and methyl isobutyl methanol.
The components may be mixed in plural or mixed with an organic solvent other than those described above.
The water content in the rinse solution is preferably 10 mass% or less, more preferably 5 mass% or less, and even more preferably 3 mass% or less. By setting the water content to 10 mass% or less, good development characteristics can be obtained.
In the rinsing step, a substrate developed with an organic developer is rinsed with a rinse solution containing an organic solvent. In addition, the rinse solution may contain an appropriate amount of surfactant.
The method of the cleaning treatment is not particularly limited, and examples thereof include the following methods: a method of continuously discharging a rinse liquid on a substrate rotating at a constant speed (spin coating method); a method of immersing the substrate in the rinse solution for a predetermined period of time (immersion method); or a method of spraying a rinse solution onto the surface of the substrate (a spraying method). Among them, the spin coating method is preferably used to perform a cleaning process, and after the cleaning, the substrate is rotated at a rotation speed of 2,000 to 4,000rpm (revolution per minute (revolutions per minute)), so that the rinse liquid is removed from the substrate. It is also preferable to include a heating step (Post bak) after the rinsing step. By this heating step, the developer and rinse remaining between and in the pattern can be removed. In the baking step after the rinsing step, the baking temperature is usually 40 to 160 ℃, preferably 70 to 95 ℃, and the baking time is usually 10 seconds to 3 minutes, preferably 30 seconds to 90 seconds.
The actinic-ray-or radiation-sensitive resin composition of the present invention and the various materials used in the pattern forming method of the present invention (for example, resist solvents, developer solutions, rinse solutions, antireflective film-forming compositions, top coat-forming compositions, and the like) preferably do not contain impurities such as metal components, isomers, and residual monomers. The content of these impurities contained in the respective materials is preferably 1ppm or less, more preferably 100ppt or less, further preferably 10ppt or less, and particularly preferably substantially none (equal to or less than the detection limit of the measuring device).
Examples of the method for removing impurities such as metals from the above-mentioned various materials include filtration using a filter. The pore size of the filter is preferably 10nm or less, more preferably 5nm or less, and even more preferably 3nm or less. The filter is preferably made of polytetrafluoroethylene, polyethylene or nylon. The filter may be made of a material which has been previously washed with an organic solvent. In the filter filtration step, a plurality of filters may be used in series or in parallel. When a plurality of filters are used, filters having different pore diameters and/or different materials may be used in combination. In addition, the various materials may be filtered a plurality of times, and the step of filtering a plurality of times may be a cyclic filtering step. As the filter, a filter in which the dissolution is reduced as disclosed in japanese patent application laid-open No. 2016-201626 (japanese patent application laid-open No. 2016-201426) is preferable.
In addition to the filter filtration, the impurities may be removed by an adsorbent, or the filter filtration and the adsorbent may be used in combination. As the adsorbent, a known adsorbent can be used, and for example, an inorganic adsorbent such as silica gel or zeolite, or an organic adsorbent such as activated carbon can be used. Examples of the metal adsorbent include adsorbents disclosed in Japanese patent application laid-open No. 2016-206500 (Japanese patent application laid-open No. 2016-206500).
As a method for reducing impurities such as metals contained in the above-mentioned various materials, the following methods are mentioned: a method of selecting a raw material having a small metal content as a raw material constituting each material, filtering the raw material constituting each material by a filter, or distilling the raw material in a device under such a condition that contamination is suppressed as much as possible by lining the device with TEFLON (registered trademark). The preferable conditions for filtering the raw materials constituting the respective materials by the filter are the same as those described above.
In order to prevent the contamination of impurities, it is preferable that the above-mentioned various materials are stored in a container described in U.S. patent application publication No. 2015/0227049, japanese patent application publication No. 2015-123351 (japanese patent application laid-open No. 2015-123351), or the like.
A method of improving the surface roughness of a pattern can be applied to a pattern formed by the pattern forming method of the present invention. As a method for improving the surface roughness of the pattern, for example, a method of treating the pattern by plasma of a gas containing hydrogen disclosed in U.S. patent application publication No. 2015/0104957 is given. In addition to these, known methods described in Japanese patent application laid-open No. 2004-235468 (Japanese patent application laid-open No. 2004-235468) and U.S. patent application laid-open No. 2010/0020297 and Proc.of SPIE Vol.8328 83280N-1"EUV Resist Curing Technique for LWR Reduction and Etch Selectivity Enhancement" can be applied.
[ method for manufacturing solid-state imaging element ]
The method for manufacturing a solid-state imaging element according to the present invention includes the above-described pattern forming method, and the method for manufacturing a solid-state imaging element includes:
(i) An ion implantation step (ion implantation step) of forming a light receiving section for sensing infrared rays by implanting ions into a non-mask region of a substrate with a pattern formed on the substrate as a mask;
(ii) A step of removing the pattern from the substrate (mask removing step); and
(iii) An infrared ray transmissive filter layer arrangement step (infrared ray transmissive filter layer arrangement step) of arranging an infrared ray transmissive filter layer on the ion implanted region of the substrate.
(i) In the ion implantation step, the film thickness of the pattern used as a mask is, for example, 2 μm or more, more preferably 5 μm or more, and still more preferably 7 μm or more. The upper limit is not particularly limited, and is, for example, 15 μm or less.
Further, as for the ion implantation step (i), a known method can be used. For example, japanese patent No. 5241883 and the like can be referred to.
Further, the mask removing step (ii) and the infrared ray transmitting filter layer disposing step (iii) can be performed by a known method. For example, japanese patent application laid-open No. 2015-063593 and the like can be referred to.
Examples
The present invention will be described in more detail with reference to examples. The materials, amounts used, ratios, processing contents, processing steps, and the like shown in the following examples can be appropriately changed without departing from the gist of the present invention. Accordingly, the scope of the present invention should not be construed in a limiting manner by the examples shown below. Unless otherwise specified, "parts" and "%" are mass references.
[ preparation of photosensitive radiation-sensitive or radiation-sensitive resin composition ]
The following shows various components contained in the actinic-ray-sensitive or radiation-sensitive resin compositions shown in table 1.
< preparation of actinic-ray-or radiation-sensitive resin composition >
The components shown in table 1 were mixed to the solid content concentrations shown in table 1. Next, the obtained mixed liquid was filtered using a polyethylene filter having a pore size of 3 μm, whereby a actinic ray-sensitive or radiation-sensitive resin composition (hereinafter, also referred to as "resist composition") was prepared. In the resist composition, the solid component means all components except the solvent. The solid content concentration of the resist composition was adjusted by the content of the solvent, and the film thickness was adjusted as shown in table 2.
The obtained resist compositions were used in examples and comparative examples.
Further, as a result of measuring the amounts of 25 (Na, K, ca, fe, cu, mg, mn, al, li, cr, ni, sn, zn, ag, as, au, ba, cd, co, pb, ti, V, W, mo, zr) metal impurity components contained in the obtained resist composition by means of an ICP-MS apparatus (inductively coupled plasma mass spectrometer (Inductively coupled plasma mass spectrometer)) "Agilent 7500cs", manufactured by Agilent Technologies, inc.
Hereinafter, various components contained in the resist compositions shown in table 1 are shown.
< resin >)
The structures of the resins a to E shown in table 1 are shown below. In addition, the weight average molecular weight (Mw), the dispersity (Mw/Mn), and the glass transition temperature (Tg (. Degree. C.) of the resins A to E are shown in Table 1.
The weight average molecular weights (Mw) and the dispersibilities (Mw/Mn) of the resins A to E were measured by GPC (carrier: tetrahydrofuran (THF)) as polystyrene conversion values, and the composition ratios (mole% ratios) of the resins A to E were determined by 13 C-NMR (nuclear magnetic resonance: nuclear magnetic resonance) was measured.
The glass transition temperatures (Tg (. Degree. C.) of the resins A to E were measured by DSC method. As a DSC device, "thermal analysis DSC differential scanning calorimeter Q1000 type" manufactured by TA Instruments Japan inc. Was used, and measurement was performed at a temperature rising rate of 10 ℃/min.
Hereinafter, the monomer structures used for the synthesis of the resins a to E are shown.
PHS: para-hydroxystyrene
TBm: tertiary butyl methacrylate
St: styrene
Bzm: benzyl methacrylate
Bza: benzyl acrylate
2EtHx: 2-ethylhexyl methacrylate
TBa: acrylic acid tert-butyl ester
The specific structures of the resins a to E are shown below.
[ chemical formula 33]
< specific additive >)
The structures of the specific additives shown in table 1 are shown below. The specific additives shown below are all water-soluble.
Tetraethyleneglycol dimethyl ether
[ chemical formula 34]
Tripropylene glycol
[ chemical formula 35]
< photoacid generator >)
The structure of the photoacid generator shown in table 1 is shown below.
[ chemical formula 36]
< acid diffusion controlling agent >)
The structure of the acid diffusion controlling agent shown in table 1 is shown below.
[ chemical formula 37]
< surfactant >)
The structure of the surfactant shown in table 1 is shown below.
MEGAFACE R-41, DIC CORPORATION manufacture
< solvent >
The solvents shown in table 1 are shown below.
PGME: propylene glycol monomethyl ether
PGMEA: propylene glycol monomethyl ether acetate
In table 1, the content (mass%) of each component is the content relative to the total solid component.
TABLE 1
[ various evaluations ]
The following measurements were performed using the resist compositions of examples and comparative examples.
(film Density (g/cm) 3 ) Is a measurement of (2)
The resist composition was applied dropwise to an 8 inch Si substrate (manufactured by Advanced Materials Technology (hereinafter also referred to as "substrate") treated with hexamethyldisilazane using a spin coater "ACT-8" manufactured by Tokyo Electron Limited, while the substrate was stationary, without providing an antireflection layer. After the dropping, the substrate was rotated, and the rotation speed was maintained at 500rpm for 3 seconds, then at 100rpm for 2 seconds, then at 500rpm for 3 seconds, then at 100rpm for 2 seconds, and then the rotation speed was increased to the film thickness setting rotation speed (for example, the rotation speed at which the film thickness was 9 μm) and maintained for 60 seconds. Then, baking and drying were performed on a baking plate at 150℃for 90 seconds, to form a film having a film thickness of 9. Mu.m.
Next, the film density was calculated for the film having a film thickness of 9 μm obtained by performing the following measurement.
(1) The volume V (cm) of the film was calculated from the film area (area of the film-forming region) and the film thickness (9 μm) on the substrate 3 )。
(2) The total mass W1 (g) of the substrate and the film was measured.
(3) The film on the substrate was removed (dissolved and/or peeled) using methanol, and the mass W2 (g) of the substrate after the film was removed was measured.
(4) The mass W (g) of the film was obtained by subtracting W2 from W1 (W (g) =w1 (g) -W2 (g)).
(5) The film density T (T (g/cm) at a film thickness of 9 μm was obtained by dividing W by V 3 )＝W(g)/V(cm 3 ))。
The results are shown in Table 2.
(measurement of residual solvent amount (%)
The resist composition was dropped onto an 8 inch Si substrate (manufactured by Advanced Materials Technology corporation (hereinafter also referred to as "substrate") using a spin coater "ACT-8" manufactured by Tokyo Electron Limited in a state where the substrate was stationary without providing an antireflection layer. After the dropping, the substrate was rotated, and the rotation speed was maintained at 500rpm for 3 seconds, then at 100rpm for 2 seconds, then at 500rpm for 3 seconds, then at 100rpm for 2 seconds, and then the rotation speed was increased to the film thickness setting rotation speed (for example, the rotation speed at which the film thickness was 9 μm) and maintained for 60 seconds. Then, baking and drying were performed on a baking plate at 150℃for 90 seconds, to form a film having a film thickness of 9. Mu.m.
Then, the residual solvent (%) in the film was calculated by measuring a sample solution obtained by peeling and dissolving the film having a film thickness of 9 μm from the substrate with a certain amount of methanol by using a gas chromatography apparatus.
The results are shown in Table 2.
(evaluation of ion leakage upon ion injection)
The resist composition prepared in the above was applied dropwise to an 8 inch Si substrate (Advanced Materials Technology (hereinafter also referred to as "substrate") treated with hexamethyldisilazane without providing an antireflection layer, using a spin coater "ACT-8" manufactured by Tokyo Electron Limited, while leaving the substrate standing. After the dropping, the substrate was rotated, and the rotation speed was maintained at 500rpm for 3 seconds, then at 100rpm for 2 seconds, then at 500rpm for 3 seconds, then at 100rpm for 2 seconds, and then the rotation speed was increased to the film thickness setting rotation speed (for example, the rotation speed to be the film thickness described in table 2) and maintained for 60 seconds. Then, baking and drying were performed on a baking plate at 150℃for 90 seconds, to form resist films having film thicknesses (. Mu.m) shown in Table 2.
Through the above steps, a wafer with a resist film having a substrate and a solid film of the resist film formed on the substrate was obtained. The wafer with the resist film was used as an evaluation wafer without performing exposure and development processes.
Then, ion implantation was performed on the evaluation wafer, and ion leakage to the substrate was evaluated.
Specifically, the doping amount was 2×10 by ion implantation 13 cm -2 After phosphorus was implanted at 80KeV, the mask was stripped. Then, the sample injection amount of phosphorus into the substrate was quantified by dynamic SIMS (Secondary Ion Mass Spectrometry: secondary ion mass spectrometry) analysis. The values of the examples and comparative examples are normalized by taking the value of example 1 as 1 (reference).
The results are shown in Table 2.
TABLE 2
From the results of table 2, it was confirmed that ion leakage was further suppressed at the time of ion implantation according to the pattern formed from the resist composition of the example containing a specified amount of the specific additive.
Further, from the comparison of examples 1 to 6, it was confirmed that when the film density was 1.10 or more, ion leakage was further suppressed at the time of ion implantation.
Further, from the comparison of examples 1 to 6, it was confirmed that the film density of the formed pattern was further improved by including a reactive group (e.g., OH group) capable of reacting with the resin in the molecule by the specific additive.
(evaluation of Pattern formation)
The resin composition prepared in the above was dropped onto an 8 inch Si substrate (manufactured by Advanced Materials Technology company (hereinafter also referred to as "substrate") subjected to hexamethyldisilazane treatment, without providing an antireflection layer, using a spin coater "ACT-8" manufactured by Tokyo Electron Limited, while leaving the substrate standing. After the dropping, the substrate was rotated, and the rotation speed was maintained at 500rpm for 3 seconds, then at 100rpm for 2 seconds, then at 500rpm for 3 seconds, then at 100rpm for 2 seconds, and then the rotation speed was increased to the film thickness setting rotation speed (for example, the rotation speed to be the film thickness described in table 2) and maintained for 60 seconds. Then, baking and drying were performed on a baking plate at 150℃for 90 seconds, to form resist films having film thicknesses (. Mu.m) shown in Table 2.
The resist film was subjected to pattern exposure using a KrF excimer laser scanner (manufactured by ASML, PAS5500/850C wavelength 248 nm) under exposure conditions of na=0.60 and σ=0.75 through a mask having a line and space pattern (line and space) in which the space width of the pattern formed after the reduced projection exposure and development was 5 μm and the pitch width was 25 μm. After the irradiation, baking was performed at 120℃for 60 seconds, after immersing for 60 seconds with a 2.38 mass% aqueous solution of tetramethylammonium hydroxide (TMAH), rinsing with pure water for 30 seconds and drying, and then baking was performed at 110℃for 60 seconds, thereby forming an isolated space pattern having a space width of 5 μm and a pitch width of 25. Mu.m.
The resist compositions of examples 1 to 6 each confirmed that a pattern having excellent linearity could be formed.

Claims (14)

1. A actinic-ray-or radiation-sensitive resin composition for forming a pattern to be used as a mask in an ion implantation process, the composition comprising:
a resin comprising a repeating unit having an acid-decomposable group and a repeating unit represented by the following general formula (1);
a photoacid generator; and
An additive having a melting point or glass transition temperature of less than 25 ℃, a molecular weight of 180 or more, and a poly (oxyalkylene) structure,
the content of the additive is 1% by mass or more relative to the total solid content in the composition,
the general formula (1) is:
in the general formula (1), R 1 Represents a hydrogen atom, a halogen atom or an alkyl group, R 2 Represents a non-acid-decomposable chain alkyl group having 2 or more carbon atoms, optionally containing a heteroatom.
2. The actinic-ray-or radiation-sensitive resin composition according to claim 1, wherein,
the film thickness of the pattern is 5 μm or more.
3. The actinic-ray-or radiation-sensitive resin composition according to claim 1 or 2, wherein,
the film thickness of the pattern is 7 μm or more.
4. The actinic-ray-or radiation-sensitive resin composition according to claim 1 or 2, wherein,
The concentration of the solid content in the composition is 20% by mass or more.
5. The actinic-ray-or radiation-sensitive resin composition according to claim 1 or 2, wherein,
a film density of 1.05g/cm of a film having a film thickness of 9 μm obtained by baking the coating film at 150℃for 90 seconds after forming the coating film by applying the actinic ray-or radiation-sensitive resin composition on a substrate 3 The above.
6. The actinic-ray-or radiation-sensitive resin composition according to claim 5, wherein,
the film density was 1.10g/cm 3 The above.
7. The actinic-ray-or radiation-sensitive resin composition according to claim 1 or 2, wherein,
the glass transition temperature of the resin is below 170 ℃.
8. The actinic-ray-or radiation-sensitive resin composition according to claim 1 or 2, wherein,
the additive is water-soluble.
9. The actinic-ray-or radiation-sensitive resin composition according to claim 1 or 2, wherein,
the ion implantation step is an ion implantation step for forming a light receiving section for an infrared ray transmission filter in manufacturing a solid-state imaging element including the infrared ray transmission filter that selectively transmits an infrared ray component.
10. The actinic-ray-or radiation-sensitive resin composition according to claim 1 or 2, wherein,
the photoacid generator comprises a compound represented by the following general formula (ZI-3),
in the general formula (ZI-3),
R 1c ～R 5c each independently represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, an alkoxy group, an aryloxy group, an alkoxycarbonyl group, an alkylcarbonyloxy group, a cycloalkylcarbonyloxy group, a halogen atom, a hydroxyl group, a nitro group, an alkylthio group or an arylthio group,
R 6c r is R 7c Each independently represents a hydrogen atom, an alkyl group, a cycloalkyl group, a halogen atom, a cyano group or an aryl group,
R x r is R y Each independently represents alkyl, cycloalkyl, 2-oxoalkyl, 2-oxocycloalkaneA group, alkoxycarbonylalkyl, allyl or vinyl group,
R 1c ～R 5c more than 2 of any one of R 5c And R is R 6c 、R 6c And R is R 7c 、R 5c And R is R x And R is x And R is R y Optionally each bonded to form a ring structure,
Zc - representing anions.
11. The actinic-ray-or radiation-sensitive resin composition according to claim 1 or 2, wherein,
also comprises an acid diffusion control agent represented by the following general formula (6),
in the general formula (6),
l represents an integer of 0 to 2, m represents an integer of 1 to 3, satisfying l+m=3,
R a represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group or an aralkyl group, and when l is 2, 2R' s a Optionally identical or different, 2R a Optionally linked to each other to form, together with the nitrogen atom of the formula, a heterocyclic ring optionally containing a heteroatom other than the nitrogen atom of the formula,
R b each independently represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group or an alkoxyalkyl group, R b Optionally linked to each other to form a ring.
12. A resist film formed from the actinic-ray-or radiation-sensitive resin composition according to any one of claims 1 to 11.
13. A pattern forming method, comprising:
a resist film forming step of forming a resist film using the actinic-ray-or radiation-sensitive resin composition according to any one of claims 1 to 11;
an exposure step of exposing the resist film; and
And a developing step of developing the exposed resist film using a developing solution.
14. A manufacturing method of a solid-state imaging element, comprising the pattern forming method according to claim 13, the manufacturing method comprising:
an ion implantation step of forming a light receiving section for sensing infrared rays by implanting ions into a non-mask region of a substrate with the pattern formed on the substrate as a mask;
A step of removing the pattern from the substrate; and
An infrared ray transmission filter layer arrangement step of arranging an infrared ray transmission filter layer on the ion-implanted region of the substrate.
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